Phenylacetylene derivatives

ABSTRACT

The invention is related to a novel phenylacetylene derivates of formula: ##STR1## wherein X represents hydrogen, halogen, optionally substituted C 1-6  alkyl; Y represents hydrogen, halogen, cyano, nitro, optionally substituted C 1-6  alkyl, C 1-6  alkoxy, C 3-8  cycloalkoxy, optionally substituted C 1-6  alkylthio, C 3-8  cycloalkylthio, C 1-6  alkylsulfinyl, optionally substituted C 1-6  alkylsulfonyl, C 3-8  cycloalkylsulfonyl, C 1-6  alkylsulfonyloxy, optionally substituted sulfonamide, optionally substituted carboxamide, etc., or Y may form together with Z which is bonded to the vicinal carbon atom a 5- or 6-membered ring; n is 0 or 1; Z represents hydrogen or halogen; m is 1 or 2; R represents hydrogen, halogen, C 1-6  alkyl, tri(C 1-6  alkyl)silyl, COOR c  or CONR d  R e  ; Q represents a heterocyclic group, and their use as herbicid.

The present invention relates to novel phenylacetylene derivatives, toprocesses for their preparation and to their use as herbicides.

It has already been known that certain heterocyclic compounds comprisinga substituted phenyl moiety have herbicidal activity (see e.g. JapanesePatent Official Announcement (kohyo) Hei 2-501309; Japanese Patent KokaiPublications Sho 60-172967, Sho 61-2659, Sho 61-43188, Sho 61-212558,Sho 62-181283, Sho 63-152366, Sho 63-230678, Sho 63-313779, Hei 1-56674,Hei 1-199978, Hei 4-117355, Hei 4-217968, Hei 6-321941, Hei 7-89313, Hei7-89941, Hei i-187919, Hei 7-188220, Hei 7-188221, Hei 8-253476, Hei8-259546; EP-A 361114; DE-A 1695840, DE-A 2612731; FR-A 2660308, U.S.Pat. No. 5,136,868, U.S. Pat. No. 5,310,723, WO90/06748, WO94/0451 1,WO94/13652, WO95/33718, WO95/33719).

There have now been found novel phenylacetylene derivatives of formula(I). ##STR2## wherein X represents hydrogen, halogen, C₁₋₆ alkyl or C₁₋₆haloalkyl,

Y represents hydrogen, hydroxy, halogen, cyano, nitro, C₁₋₆ alkyl C₁₋₆haloalkyl, C₁₋₆ alkoxy, C₃₋₈ cycloalkoxy, C₁₋₆ haloalkoxy, C₁₋₃alkoxy-C₁₋₃ alkoxy, C₁₋₆ alkylthio, C₃₋₈ cycloalkylthio, C₁₋₆haloalkylthio, C₁₋₆ alkylsulfinyl, C₁₋₆ alkylsulfonyl, C₃₋₈cycloalkylsulfonyl, C₁₋₆ haloalkylsulfonyl, C₁₋₆ alkylsulfonyloxy, C₃₋₆alkenyloxy, C₃₋₆ alkynyloxy, a group SO₂ NR^(a) R^(b), a group COOR^(c),a group CONR^(d) R^(e), optionally substituted amino, a group A¹--(CH₂)n--CHR^(f) --COOR^(g), C₁₋₃ alkoxycarbonyl-C₁₋₃ alkyl or C₁₋₃alkoxycarbonyl-C₁₋₃ haloalkyl, or

Y may form a 5- or 6-membered ring together with Z which is vicinal tothe carbon atom of Y,

R^(a) and R^(b) each represent independently hydrogen or C₁₋₆ alkyl, or

R^(a) and R^(b) may form together with the N atom to which they arebonded a 5- or 6-membered heterocyclic group,

R^(c) represents hydrogen, an alkali metal, an alkaline earth metal,C₁₋₆ alkyl or C₁₋₄ alkoxy-carbonyl-C₁₋₄ alkyl,

R^(d) represents hydrogen or C₁₋₆ alkyl,

R^(e) represents hydrogen or C₁₋₆ alkyl,

R^(f) represents hydrogen, halogen or C₁₋₆ alkyl,

R^(g) represents hydrogen, an alkali metal, an alkaline earth metal orC₁₋₆ alkyl

A¹ represents oxygen or sulfur,

n is 0 or 1,

Z represents hydrogen or halogen,

m is 1 or 2,

R represents hydrogen, halogen, C₁₋₆ alkyl, hydroxy-C₁₋₆ alkyl, tri(C₁₋₆alkyl)silyl, a group COOR^(c) or a group CONR^(d) R^(e), ##STR3## R²represents hydrogen or C₁₋₆ haloalkyl, R³ represents hydrogen, cyano,halogen or C₁₋₆ alkyl,

R⁴ represents hydrogen, amino or C₁₋₆ alkyl,

R⁵ represents hydrogen, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₃₋₈ cycloalkyl orC₃₋₈ alkynyl,

R⁶ represents hydrogen C₁₋₆ alkyl, C₁₋₆ haloalkyl or C₁₋₃ alkoxy-C₁₋₃alkyl,

R⁷ represents hydrogen, halogen, amino, cyano, C₁₋₆ alkyl or C₁₋₆haloalkyl,

R⁸ represents hydrogen, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₁₋₆ alkoxy, C₁₋₆alkylthio, C₁₋₆ haloalkoxy, C₁₋₆ haloalkylthio, or C₃₋₈ cycloalkyl,

R⁹ represents hydrogen, C₁₋₆ alkyl or C₁₋₆ haloalkyl,

R¹⁰ represents hydrogen or C₁₋₆ alkyl,

R¹¹ represents hydrogen, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₃₋₈ alkynyl orC₃₋₈ cycloalkyl,

R¹² represents hydrogen, halogen, cyano or amino,

R¹³ represents halogen, a group A¹ --CHR¹⁰ R¹⁴ or a group NR¹⁰ R¹⁴,

R¹⁴ represents hydrogen, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₃₋₈ cycloalkyl,optionally substituted phenyl or an optionally substituted 5- or6-membered heterocyclic group,

R¹⁵ represents halogen or OR¹⁶,

R¹⁶ represents hydrogen or acyl,

R¹⁷ and R¹⁸ each represent independently hydrogen or C₁₋₆ alkyl,

R¹⁹ and R²⁰ each represent independently represent hydrogen, C₁₋₆ alkyl,C₁₋₆ haloalkyl or C₃₋₈ cycloalkyl,

R²¹ represents hydrogen or C₁₋₆ alkyl,

R²² represents hydrogen, C₁₋₆ alkyl or C₁₋₆ haloalkyl,

R²³ hydrogen, halogen, cyano, optionally substituted phenyl or a radicalCONR^(d) R^(e),

R²⁴ represents C₁₋₆ alkyl, C₁₋₆ haloalkyl, optionally substituted phenylor C₃₋₈ cycloalkyl,

R²⁵ represents cyano or a radical CONR^(d) R^(e),

R²⁶ represents C₁₋₆ allyl, C₁₋₆ haloalkyl, C₃₋₆ cycloalkyl, C₁₋₃alkyl-C₃₋₆ cycloalkyl, 1-cyano-C₃₋₆ cycloalkyl, 1-amino-C₃₋₆ cycloalkyl,1-ethynyl-C₃₋₆ cycloalkyl, 1-cyano-C₃₋₅ alkyl or 1-ethynyl-C₃₋₅ alkyl,

R²⁷ represents hydrogen, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₃₋₆ cycloalkyl,C₁₋₆ alkoxy, C₁₋₆ haloalkoxy or C₃₋₆ cycloalkyl-C₁₋₄ alkoxy,

R²⁸ represents hydrogen or halogen,

A² represents oxygen or sulfur, and

A³ represents oxygen, sulfur or CH₂.

The phenylacetylene derivatives of formula (I) according to theinvention can be obtained by the following processes:

(a) In the case where R is a group other than hydrogen:

compounds of formula (II) ##STR4## wherein X, Y, Z, m and Q are definedas above, and hal is bromine or iodine, are reacted with compounds offormula (III)

    R'--C.tbd.CH                                               (III)

wherein R' represents a group as defined for the above R with theexception of hydrogen, if appropriate, in the presence of inertsolvents, a catalyst, a promoter and an acid binder, or

(b) in the case where R is hydrogen:

compounds of formula (Ia) ##STR5## wherein X, Y, Z, m and Q are definedas above are reacted with a desilylating agent in the presence ofappropriate diluents.

The phenylacetylene derivatives of formula (I) according to theinvention, exhibit powerful herbicidal effects.

Surprisingly, the phenylacetylene derivatives of formula (I) provided bythe invention exhibit substantially superior herbicidal effects incomparison with the previously known compounds described in the aboveprior art literature.

In this specification, the "halogen" and the halogen atoms in the"haloalkyl", "haloalkoxy", "haloalkylthio" and "haloalkylsulfonyl"radicals represent fluorine, chlorine, bromine or iodine, preferablybeing fluorine, chlorine or bromine.

When these "haloalkyl", "haloalkoxy", "haloalkylthio" and"haloalkylsulfonyl" radicals contain two or more halogen atoms, thesehalogen atoms may be same or different.

The "alkyl" may be straight-chain or branched and includes, for example,methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl,tert-butyl, pentyl, neopentyl, hexyl, 2-ethylhexyl, and the like.

The "haloalkyl" may be straight-chain or branched and includes, forexample, chloromethyl, trichloro-methyl, difluoromethyl,trifluoromethyl, chlorodifluoromethyl, 2,2,2-trifluoroethyl,3-fluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3-tetrafluoropropyl,1,1,2,3,3,3-hexafluoropropyl, 2-chloro-1,1-dimethylethyl,2-fluoro-1,1-dimethylethyl, and the like.

The "alkoxy" may be straight-chain or branched and includes, forexample, methoxy, ethoxy, isopropoxy, propoxy, butoxy, isobutoxy,tert-butoxy; pentoxy, and the like.

The "cycloalkyl" includes, for example, cyclopropyl,1-methylcyclopropyl, 2-methylcyclopropyl, cyclobutyl, cyclopentyl,2-methylcyclopentyl, 3-methylcyclopentyl, cyclohexyl,2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, cycloheptyl,cyclooctyl, and the like.

The "cycloalkoxy" includes, for example, cyclopropyloxy,1-methylcyclopropyloxy, 2-methylcyclo-propyloxy, cyclobutyloxy,cyclopentyloxy, 2-methylcyclopentyloxy, 3-methylcyclopentyloxy,cyclohexyloxy, 2-methylcyclohexyloxy, 3-methylcyclohexyloxy,4-methylcyclohexyloxy, cycloheptyloxy, cyclooctyloxy, and the like.

The "haloalkoxy" may be straight-chain or branched and includes, forexample, difluoromethoxy, trifluoromethoxy,2-chloro-1,1,2-trifluoroethoxy, 2,2,2-trifluoroethoxy, and the like.

The "alkylthio" may be straight-chain or branched and includes, forexample, methylthio, ethylthio, propylthio, isopropylthio, butylthio,isobutylthio, sec-butylthio, tert-butylthio, pentylthio, neopentylthio,hexylthio, 2-ethylhexylthio, and the like.

The "cycloalkythio" includes, for example, cyclopropylthio,1-methylcyclopropylthio, cyclopentylthio, 1-methylcyclopentylthio,cyclohexylthio, 1-methylcyclohexylthio, 2-methylcyclohexylthio,3-methyl-cyclohexylthio, cycloheptylthio, cyclooctylthio, and 5 thelike.

The "haloalkylthio" may be straight-chain or branched and includes, forexample, difluoromethylthio, chlorodifluoromethylthio,trifluoromethylthio, 2,2,2-trifluoroethylthio, 3-fluoropropylthio,3,3,3-trifluoropropylthio, 2,2,3,3-tetrafluoropropylthio,1,1,2,3,3,3-hexafluoropropylthio, 2-chloro-1,1-dimethylethylthio,2-fluoro-1,1-dimethylethylthio, and the like.

The "alkylsulfinyl" may be straight-chain or branched and includes, forexample, methylsulfinyl, ethylsulfinyl, propylsulfinylisopropylsulfinyl, butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl,tert-butylsulfinyl, pentylsulfinyl, neopentylsulfinyl, hexylsulfinyl,2-ethylhexylsulfinyl, and the like.

The "alkylsulfonyl" may be straight-chain or branched and includes, forexample, methylsulfonyl, ethylsulfonyl, propylsulfonyl,.isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl,tert-butylsulfonyl, pentylsulfonyl neopentylsulfonyl, hexylsulfonyl,2-ethylhexylsulfonyl, and the like.

The "cycloalkylsulfonyl" includes, for example, cyclopropylsulfonyl1-methylcyclopropylsulfonyl, cyclobutylsulfonyl, cyclopentylsulfonyl,cyclohexylsulfonyl, 1-methylcyclohexylsulfonyl, cycloheptylsulfonyl,cyclooctylsulfonyl, and the like.

The "haloalkylsulfonyl" may be straight-chain or branched and includes,for example, difluoromethylsulfonyl, chlorodifluoromethylsulfonyl,trifluoromethylsulfonyl, and the like.

The "alkylsulfonyloxy" may be straight-chain or branched and includes,for example, methylsulfonyl-oxy, ethylsulfonyloxy, propylsulfonyloxy,isopropylsulfonyloxy, butylsulfonyloxy, isobutylsulfonyl-oxy,sec-butylsulfonyloxy, tert-butylsulfonyloxy, pentylsulfonyloxy,neopentylsulfonyloxy, hexyl-sulfonyloxy, and the like.

The "alkenyloxy" may be straight-chain or branched and includes, forexample, allyloxy, butenyloxy, 2-methylallyloxy, and the like.

The "alkynyloxy" may be straight-chain or branched and includes, forexample, propargyloxy, and the like.

The "amino" may optionally be mono- or di-substituted by substituent(s)such as C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₂₋₆ alkylcarbonyl C₁₋₆alkysulfonyl, C₃₋₆ cycloalkylsulfonyl, C₁₋₆ haloalkyl-sulfonyl, C₂₋₆alkenyl and C₂₋₆ alkynyl and includes, for example, amino, acetylamino,trifluoromethylsulfonylamino, methylsulfonylamino, ethylsulfonylamino,bis(methylsulfonyl)amino, 2,2,2-trifluoroethyl-sulfonylamino,N-2-propynyl-N-ethylsulfonylamino, N-2-propenyl-N-ethyl-sulfonylamino,N-methyl-N-ethylsulfonylamino, N-acetyl-N-ethylsulfonylamino, and thelike.

The "phenyl" may optionally be substituted by one or more ofsubstituent(s) and examples of the substituents include halogen(fluorine, chlorine, bromine, iodine), C₁₋₆ alkyl (e.g., methyl, ethyl,propyl, isopropyl, butyl), C₁₋₆ haloalkyl (e.g., chloromethyl,trichloromethyl, difluoromethyl, trifluoromethyl, chlorodifluoromethyl,2,2,2-trifluoroethyl, 3-fluoropropyl, 3,3,3-trifluoropropyl,2,2,3,3-tetrafluoropropyl, 1,1,2,3,3,3,-hexafluoropropyl, and the like.

The "5- or 6-membered heterocyclic group" may contain one to fourheteroatoms selected from N, S and O in the ring and includes, forinstance, pyrazolyl, isoxazolyl, thienyl, pyridyl, and the like. Theseheterocyclic groups may be substituted by one or more substituent(s) andexamples of the substituents include halogen (fluorine, chlorine,bromine, iodine), C₁₋₆ alkyl (e.g., methyl, ethyl, propyl, isopropyl,butyl), C₁₋₆ haloalkyl (e.g., chloromethyl, trichloromethyl,difluoromethyl, trifluoromethyl, chlorodifluoromethyl,2,2,2-trifluoroethyl, 3-fluoropropyl, 3,3,3-trifluoropropyl,2,2,3,3-tetrafluoropropyl, 1,1,2,3,3,3,-hexafluoropropyl), and the like.

Among the compounds of formula (I) according to the invention, preferredphenylacetylene derivatives of formula (I) are those wherein

X represents hydrogen, fluorine, chlorine, methyl or trifluoromethyl,

Y represents hydrogen, hydroxy, fluorine, chlorine, cyano, nitro,methyl, ethyl, propyl, trifluoromethyl, chlorodifluoromethyl, C₁₋₃alkoxy, C₃₋₆ cycloalkoxy, C₁₋₃ haloalkoxy, C₁₋₃ alkoxy-C₁₋₃ alkoxy, C₁₋₃alkylthio, C₃₋₆ cycloalkylthio, C₁₋₃ haloalkyithio, C₁₋₃ alkyl-sulfinyl,C₁₋₃ alkylsulfonyl, C₃₋₆ cycloalkylsulfonyl, C₁₋₃ haloalkylsulfonyl,C₁₋₃ alkylsulfonyl-oxy, C₃₋₄ alkenyloxy, C₃₋₄ alkynyloxy, aminosulfonyl,methyl-aminosulfonyl, ethylamino-sulfonyl, diethylaminosulfonyl,1-pyrrolidinyl-sulfonyl, a group COORC, aminocarbonyl, amino,acetylamino, trifluoromethylsulfonylamino, methylsulfonylamino,ethylsulfonylamino, bis(methylsulfonyl)amino, bis(ethylsulfonyl)amino,(C₁₋₄ alkylcarbonyl)(C₁₋₄ alkyl-sufonyl)amino, C₁₋₃ alkoxycarbonyl-C₁₋₃alkylthio, C₁₋₃ alkoxy-carbonyl-C₁₋₃ haloalkyl-thio, C₁₋₃alkoxycarbonyl-C₁₋₃ alkoxy, C₁₋₃ alkoxy-carbonyl-C₁₋₃ haloalkoxy, C₁₋₃alkoxycarbonyl-C₁₋₃ alkyl or C₁₋₃ alkoxycarbonyl-C₁₋₃ haloalkyl,

R^(c) represents hydrogen, methyl, ethyl, propyl, methoxycarbonylmethyl,ethoxycarbonylmethyl, 1-(methoxycarbonyl)ethyl or1-(ethoxycarbonyl)ethyl,

A¹ represents oxygen or sulfur,

n is 0 or 1,

Z represents hydrogen, fluorine or chlorine, or

Y may form a group --OCR^(h) R^(i) --CH₂ -- or a group --OCR^(h) ═CH--together with Z which is vicinal to the carbon atom of Y,

R^(h) represents hydrogen, C₁₋₃ alkyl, hydroxy-C₁₋₃ alkyl, C₁₋₃alkoxy-C₁₋₃ alkyl, carboxy or C₁₋₃ alkoxycarbonyl,

R^(i) represents hydrogen or C₁₋₃ alkyl,

m is 1 or 2,

R represents hydrogen, fluorine, methyl, hydroxymethyl, trimethylsilyl,methoxycarbonyl, ethoxycarbonyl or aminocarbonyl, ##STR6## R² representshydrogen, trifluoromethyl, difluoromethyl, chlorodifluoromethyl,2,2,2-trifluoroethyl, 3-fluoro-propyl, 3,3,3-trifluoropropyl,2,2,3,3-tetrafluoropropyl or 1,1,2,3,3,3-hexafluoropropyl,

R³ represents hydrogen, cyano, fluorine, chlorine, methyl or ethyl,

R⁴ represents hydrogen, amino, methyl or ethyl,

R⁵ represents hydrogen, methyl, ethyl, isopropyl, tert-butyl,1-ethyl-1-methylpropyl, 1,1-dimethylpropyl, chloromethyl,difluoromethyl, dichlorofluoromethyl, trifluoromethyl, 3-fluoropropyl,1,1-dimethyl-2-chloroethyl, 1,1-dimethyl-2-fluoroethyl, cyclopropyl or1,1-dimethylpropargyl,

R⁶ represents hydrogen, methyl, ethyl, propyl, isopropyl, tert-butyl,2,2,2-trifluoroethyl, methoxymethyl, methoxyethyl or ethoxyethyl,

R⁷ represents hydrogen, fluorine, chlorine, amino, cyano, methyl, ethyl,difluoromethyl, chlorodifluoromethyl or trifluoromethyl,

R⁸ represents hydrogen, methyl, ethyl, propyl, isopropyl, tert-butyl,difluoromethyl, chlorodifluoromethyl, trifluoromethylmethoxy, ethoxy,isopropoxy, tert-butoxy, methylthio, ethylthio, propylthio,isopropylthio, difluoromethylthio, chlorodifluoromethylthio,trifluoromethylthio, 3-fluoropropylthio or cyclopropyl,

R⁹ represents hydrogen, methyl, ethyl, propyl, isopropyl, tert-butyl,1-ethyl-1-methylpropyl, 1,1-dimethylpropyl, difluoromethyl,chlorodifluoromethyl or trifluoromethyl,

R¹⁰ represents hydrogen, methyl ethyl, propyl or isopropyl

R¹¹ represents hydrogen, methyl, ethyl, propyl, isopropyl tert-butyl1-ethyl-1-methylpropyl, 1,1-dimethyl-propyl, difluoromethylchlorodifluoromethyl. trifluoromethyl, 1,1-dimethylpropargyl orcyclopropyl,

R¹² represents hydrogen, fluorine, chlorine, cyano or amino,

R¹³ represents chlorine, bromine, a group Al--CHR¹⁰ R¹⁴ or a group NR¹⁰R¹⁴,

R¹⁴ represents hydrogen, methyl, ethyl, propyl, isopropyl,difluoromethyl, chlorodifluoromethyl, trifluoro-methyl, cyclopropyl,optionally substituted phenyl wherein the substituents are selected fromthe group consisting of fluorine, chlorine and trifluoromethyl,optionally substituted pyrazolyl wherein the substituents are selectedfrom the group consisting of fluorine, chlorine, methyl andtrifluoromethyl, optionally substituted isoxazolyl wherein thesubstituents are selected from the group consisting of fluorine,chlorine, methyl and trifluoromethyl, optionally substituted thienylwherein the substituents are selected from the group consisting offluorine, chlorine, methyl and trifluoromethyl or optionally substitutedpyridyl wherein the substituents are selected from the group consistingof fluorine, chlorine, methyl and trifluoromethyl,

R¹⁵ represents fluorine, chlorine or OR¹⁶,

R¹⁶ represents hydrogen, acetyl or benzoyl,

R¹⁷ and R¹⁸ each represent independently methyl, ethyl or isopropyl

R¹⁹ and R²⁰ each represent independently hydrogen, methyl, ethyl,isopropyl, difluoromethyl, chlorodifluoromethyl, trifluoromethyl orcyclopropyl,

R²¹ represents hydrogen, methyl or ethyl,

R²² represents hydrogen, methyl, ethyl or trifluoromethyl

R²³ represents hydrogen, fluorine, chlorine, cyano, optionallysubstituted phenyl wherein the substituents are selected from the groupconsisting of fluorine, chlorine and trifluoromethyl, aminocarbonyl,methylaminocarbonyl or ethylaminocarbonyl,

R²⁴ represents methyl, ethyl, isopropyl tert-butyl, trifluoromethyloptionally substituted phenyl wherein the substituents are selected fromthe group consisting of fluorine, chlorine and trifluoromethyl orcyclopropyl,

R²⁵ represents cyano or aminocarbonyl,

R²⁶ represents methyl, ethyl, propyl, isopropyl, tert-butyl,2,2,2-trifluoroethyl, 3-fluoropropyl, cyclopropyl, cyclopentyl,cyclohexyl, 1-methylcyclopropyl, 1-methylcyclopentyl,1-methylcyclohexyl, 1-cyanocyclopropyl, 1-cyanocyclopentyl,1-cyanocyclohexyl, 1-ethynylcyclopropyl, 1-ethynylcyclopentyl,1-ethynylcyclohexyl, 1-cyano-1-methylethyl or 1,1-dimethylpropargyl,

R²⁷ represents hydrogen, methyl, ethyl, isopropyl, tert-butyl,trifluoromethyl, cyclopropyl, cyclopentyl, methoxy, ethoxy, isopropoxy,2,2,2-trifluoroethoxy or cyclopropylmethoxy,

R²⁸ represents hydrogen, fluorine or chlorine,

A² represents oxygen or sulfur, and

A³ represents oxygen, sulfur or CH₂.

Among the phenylacetylene derivatives of formula (I) according to theinvention, more preferred compounds are those wherein

X represents hydrogen or fluorine,

Y represents hydrogen, hydroxy, fluorine, chlorine, cyano, nitro,methyl, trifluoromethyl, methoxy, ethoxy, isopropoxy, cyclopropoxy,cyclopentyloxy, cyclohexyloxy, difluoromethoxy, chlorodifluoromethoxy,trifluoromethoxy, methoxymethoxy, methylthio, ethylthio, isopropylthio,propylthio, cyclopropylthio, cyclopentylthio, difluoromethylthio,chlorodifluoromethylthio, trifluoromethylthio, methylsulfinyl,methylsulfonyl, isopropylsulfonyl, cyclopropylsulfonyl,cyclopentylsulfonyl, difluoromethylsulfonyl,chlorodifluoromethylsulfonyl, trifluoromethylonyl, methylsulfonyloxy,allyloxy, 2-methylallyloxy, propargyloxy, aminosulfonyl,methylaminosulfonyl, ethylminosulfonyl, a group COOR^(c), aminocarbonyl,amino, methylsulfonylamino, ethylsulfonylamino,bis(methylsulfonyl)amino, bis(ethylsulfonyl)amino,(acetyl)(ethylsulfonyl)amino, (tert-butylcarbonyl)(methylsulfonyl)amino, (tert-butylcarbonyl)(ethylsulfonyl)amino,1-(methoxycarbonyl)ethylthio, ethoxycarbonylmethylthio,methoxycarbonylmethylthio, 1-(ethoxycarbonyl)ethylthio,1-(methoxycarbonyl)ethoxy, ethoxycarbonylmethylthoxy,methoxycarbonylmethoxy, 2-(ethoxycarbonyl)-2-chloroethoxy,ethoxycarbonylmethyl or 2-(ethoxycarbonyl)-2-chloroethyl,

R^(c) represents hydrogen, methyl, ethyl, propyl, isopropyl,methoxycarbonylmethyl, ethoxycarbonylmethyl, 1-(methoxycarbonyl)ethyl or1-(ethoxycarbonyl)ethyl,

A¹ represents oxygen or sulfur,

n is 0 or 1,

Z represents hydrogen, fluorine or chlorine,

m is 1,

R represents hydrogen, fluorine, hydroxymethyl trimethylsilyl,methoxycarbonyl or ethoxycarbonyl, ##STR7## R² represents hydrogen,trifluoromethyl, difluoromethyl, chlorodifluoromethyl, 2,2,2-trifluoroethyl, 3-fluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3-tetrafluoropropylor 1,1,2,3,3,3-hexafluoropropyl,

R³ represents hydrogen, cyano, fluorine, chlorine, methyl or ethyl,

R⁴ represents hydrogen, amino, methyl or ethyl,

R⁵ represents hydrogen, methyl, ethyl, isopropyl, tert-butyl,1-ethyl-1-methylpropyl, 1,1-dimethylpropyl, chloromethyl,difluoromethyl, dichlorofluoromethyl, trifluoromethyl, 3-fluoropropyl,1,1-dimethyl-2-chloroethyl, 1,1-dimethyl-2-fluoroethyl, cyclopropyl or1,1-dimethylpropargyl,

R⁶ represents hydrogen, methyl, ethyl, propyl, isopropyl tert-butyl,2,2,2-trifluoroethyl, methoxymethyl methoxyethyl or ethoxyethyl

R⁷ represents hydrogen, fluorine, chlorine, amino, cyano, methyl, ethyldifluoromethyl, chlorodifluoromethyl or trifluoromethyl,

R⁸ represents hydrogen, methyl, ethyl, propyl, isopropyl, tert-butyldifluoromethyl, chlorodifluoromethyl, trifluoromethylmethoxy, ethoxy,isopropoxy, tert-butoxy, methylthio, ethylthio, propylthio,isopropylthio, difluoromethylthio, chlorodifluoromethylthio,trifuoromethylthlo, 3-fluoropropylthio or cyclopropyl,

R⁹ represents hydrogen, methyl, ethyl, propyl, isopropyl, tert-butyl,1-ethyl-1-methylpropyl, 1,1-dimethylpropyl, difluoromethyl,chlorodifluoromethyl or trifluoromethyl,

R¹⁰ represents hydrogen, methyl, ethyl, propyl or isopropyl,

R¹¹ represents hydrogen, methyl, ethyl, propyl isopropyl, tert-butyl,1-ethyl-1-methylpropyl, 1,1-dimethylpropyl, difluoromethyl,chlorodifluoromethyl, trifluoromethyl, 1,1-dimethylpropargyl orcyclopropyl,

R¹² represents hydrogen, fluorine, chlorine, cyano or amino,

R¹³ represents chlorine, bromine, a group Al--CHR¹⁰ R¹⁴ or a group NR¹⁰R¹⁴,

R¹⁴ represents hydrogen, methyl, ethyl, propyl, isopropyl,difluoromethyl, chlorodifluoromethyl, trifluoromethyl, cyclopropyl,optionally substituted phenyl wherein the substituents are selected fromthe group consisting of fluorine, chlorine and trifluoromethyl,optionally substituted pyrazolyl wherein the substituents are selectedfrom the group consisting of fluorine, chlorine, methyl andtrifluoromethyl, optionally substituted isoxazolyl wherein thesubstituents are selected from the group consisting of fluorine,chlorine, methyl and trifluoromethyl, optionally substituted thienylwherein the substituents are selected from the group consisting offluorine, chlorine, methyl and trifluoromethyl or optionally substitutedpyridyl wherein the substituents are selected from the group consistingof fluorine, chlorine, methyl and trifluoromethyl,

R¹⁵ represents fluorine, chlorine or OR¹⁶,

R¹⁶ represents hydrogen, acetyl or benzoyl,

R¹⁷ and R¹⁸ each represent independently methyl, ethyl or isopropyl,

R¹⁹ and R²⁰ each represent independently hydrogen, methyl ethyl,isopropyl, difluoromethyl, chlorodifluoromethyl, trifluoromethyl orcyclopropyl,

R²¹ represents hydrogen, methyl or ethyl,

R²² represents hydrogen, methyl, ethyl or trifluoromethyl,

R²³ represents hydrogen, fluorine, chlorine, cyano, optionallysubstituted phenyl wherein the substituents are selected from the groupconsisting of fluorine, chlorine and trifluoromethyl, aminocarbonyl,methylaminocarbonyl or ethylaminocarbonyl,

R²⁴ represents methyl, ethyl, isopropyl, tert-butyl, trifluoromethyl,optionally substituted phenyl wherein the substituents are selected fromthe group consisting of fluorine, chlorine and trifluoromethyl orcyclopropyl,

R²⁵ represents cyano or aminocarbonyl,

R²⁶ represents methyl, ethyl, propyl, isopropyl, tert-butyl,2,2,2-trifluoroethyl, 3-fluoropropyl, cyclopropyl, cyclopentyl,cyclohexyl, 1-methylcyclopropyl, 1-methylcyclopentyl,1-methylcyclohexyl, 1-cyanocyclopropyl, 1-cyanocyclopentyl,1-cyanocyclohexyl, 1-ethynylcyclopropyl, 1-ethynylcyclopentyl,1-ethynylcyclohexyl, 1-cyano-1-methylethyl or 1,1-dimethylpropargyl,

R²⁷ represents hydrogen, methyl, ethyl, isopropyl, tert-butyl,trifluoromethyl, cyclopropyl, cyclopentyl methoxy, ethoxy, isopropoxy,2,2,2-trifluoroethoxy or cyclopropylmethoxy,

R²⁸ represents hydrogen, fluorine or chlorine,

A² represents oxygen or sulfur, and

A³ represents oxygen, sulfur or CH₂.

Certain phenylacetylene derivatives of formula (I) according to theinvention are listed in the following Table 1.

                                      TABLE 1    __________________________________________________________________________    1 #STR8##    2 #STR9##    R       X    Y            Zm   R.sup.2    __________________________________________________________________________    Si(CH.sub.3).sub.3            F    OCH.sub.3    H    CHF.sub.2    Si(CH.sub.3).sub.3            F    OCH.sub.3    H    CH.sub.2 CH.sub.2 CH.sub.2 F    H       F    OCH.sub.3    H    CHF.sub.2    H       F    OCH(CH.sub.3).sub.2                              H    CH.sub.2 CH.sub.2 CH.sub.2 F    H       F    O-cyclopentyl                              H    CHF.sub.2    H       F    O-cyclopentyl                              H    CH.sub.2 CH.sub.2 CH.sub.2 F    H       F    S-cyclopentyl                              H    CH.sub.2 CH.sub.2 CH.sub.2 F    H       F    NH.sub.2     H    CH.sub.2 CH.sub.2 CH.sub.2 F    H       F    NHSO.sub.2 CH.sub.3                              H    CH.sub.2 CH.sub.2 CH.sub.2 F    H       F    NHSO.sub.2 C.sub.2 H.sub.5                              H    CH.sub.2 CH.sub.2 CH.sub.2 F    H       F    NHSO.sub.2 CH.sub.3                              H    CHF.sub.2    H       F    NHSO.sub.2 C.sub.2 H.sub.5                              H    CHF.sub.2    H       F    CO.sub.2 CH.sub.3                              H    CH.sub.2 CH.sub.2 CH.sub.2 F    H       F    CO.sub.2 CH(CH.sub.3).sub.2                              H    CHF.sub.2    H       H    CO.sub.2 CH(CH.sub.3).sub.2                              H    CH.sub.2 CH.sub.2 CH.sub.2 F    CH.sub.3            F    OCH.sub.3    H    CH.sub.2 CH.sub.2 CH.sub.2 F    CO.sub.2 C.sub.2 H.sub.5            F    OCH(CH.sub.3).sub.2                              H    CHF.sub.2    H       F    OCH.sub.2 CO.sub.2 CH.sub.3                              H    CH.sub.2 CH.sub.2 CH.sub.2 F    H       F    OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                              H    CHF.sub.2    H       F    SCH.sub.2 CO.sub.2 CH.sub.3                              H    CH.sub.2 CH.sub.2 CH.sub.2 F    Si(CH.sub.3).sub.3            F    H            H    CHF.sub.2    H       F    H            H    CH.sub.2 CH.sub.2 CH.sub.2 F    Si(CH.sub.3).sub.3            F    H            H    CH.sub.2 CH.sub.2 CH.sub.2 F    H       F    N(SO.sub.2 CH.sub.2 CH.sub.3).sub.2                              H    CH.sub.2 CH.sub.2 CH.sub.2 F    Si(CH.sub.3).sub.3            F    H            H    CH.sub.2 CH.sub.2 CH.sub.2 F    H       F    N(SO.sub.2 CH.sub.2 CH.sub.3).sub.2                              H    CH.sub.2 CH.sub.2 CH.sub.2 F    Si(CH.sub.3).sub.3            F    N(SO.sub.2 CH.sub.2 CH.sub.3).sub.2                              H    CH.sub.2 CH.sub.2 CH.sub.2 F    Si(CH.sub.3).sub.3            F    NH.sub.2     H    CH.sub.2 CH.sub.2 CH.sub.2 F    Si(CH.sub.3).sub.3            F    NO.sub.2     H    CH.sub.2 CH.sub.2 CH.sub.2 F    __________________________________________________________________________    3 #STR10##    R     X   Y         Zm  R.sup.2                                  R.sup.3                                       R.sup.4    __________________________________________________________________________    Si(CH.sub.3).sub.3          F   OCH.sub.3 H   CF.sub.3                                  H    CH.sub.3    H     F   OCH.sub.3 H   CF.sub.3                                  CH.sub.3                                       CH.sub.3    H     F   OCH(CH.sub.3).sub.2                        H   CF.sub.3                                  H    CH.sub.3    H     F   O-cyclopentyl                        H   CF.sub.3                                  H    CH.sub.3    H     H   H         H   CF.sub.3                                  H    CH.sub.3    H     F   H         H   CF.sub.3                                  H    CH.sub.3    H     F   CO.sub.2 CH(CH.sub.3).sub.2                        H   CF.sub.3                                  H    CH.sub.3    H     F   NHSO.sub.2 CH.sub.3                        H   CF.sub.3                                  CH.sub.3                                       CH.sub.3    H     F   NHSO.sub.2 C.sub.2 H.sub.5                        H   CF.sub.3                                  H    CH.sub.3    H     F   OCH(CH.sub.3).sub.2                        H   CHF.sub.2                                  H    CH.sub.3    H     F   OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                        H   CF.sub.3                                  H    CH.sub.3    H     F   OCH.sub.2 CO.sub.2 CH.sub.3                        H   CF.sub.3                                  H    CH.sub.3    Si(CH.sub.3).sub.3          F   OCH.sub.2 CO.sub.2 CH.sub.3                        H   CF.sub.3                                  H    CH.sub.3    CH.sub.3          F   OCH.sub.3 H   CF.sub.3                                  H    CH.sub.3    H     F   OCH(CH.sub.3).sub.2                        H   CClF.sub.2                                  H    CH.sub.3    __________________________________________________________________________    1 #STR11##    3 #STR12##    R        X  Y           Zm R.sup.2                                   R.sup.3                                       R.sup.4    __________________________________________________________________________    H        F  OCF.sub.3   H  CF.sub.3                                   H   CH.sub.3    H        F  OCH(CH.sub.3).sub.2                            H  CF.sub.3                                   H   NH.sub.2    H        F  OCH.sub.3   H  CF.sub.3                                   H   CH.sub.3    Si(CH.sub.3).sub.3             H  H           H  CF.sub.3                                   H   CH.sub.3    Si(CH.sub.3).sub.3             F  O-cyclopentyl                            H  CF.sub.3                                   H   CH.sub.3    Si(CH.sub.3).sub.3             F  OC.sub.2 H.sub.5                            H  CF.sub.3                                   H   CH.sub.3    H        F  OC.sub.2 H.sub.5                            H  CF.sub.3                                   H   CH.sub.3    H        Cl H           H  CF.sub.3                                   H   CH.sub.3    CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3             Cl H           H  CF.sub.3                                   H   CH.sub.3    Si(CH.sub.3).sub.3             Cl H           H  CF.sub.3                                   H   CH.sub.3    H        F  NHSO.sub.2 CH.sub.3                            H  CF.sub.3                                   H   CH.sub.3    C(CH.sub.3).sub.3             Cl H           H  CF.sub.3                                   H   CH.sub.3    H        F  OSO.sub.2 CH.sub.3                            H  CF.sub.3                                   H   CH.sub.3    H        F  N(SO.sub.2 CH.sub.3).sub.2                            H  CF.sub.3                                   H   CH.sub.3    H        F  NO.sub.2    H  CF.sub.3                                   H   CH.sub.3    H        F  OCH(CH.sub.3).sub.2                            H  CF.sub.3                                   CH.sub.3                                       CH.sub.3    Si(CH.sub.3).sub.3             F  NO.sub.2    H  CF.sub.3                                   CH.sub.3                                       CH.sub.3    H        F  NO.sub.2    H  CF.sub.3                                   CH.sub.3                                       CH.sub.3    Si(CH.sub.3).sub.3             F  NH.sub.2    H  CF.sub.3                                   CH.sub.3                                       CH.sub.3    H        F  NH.sub.2    H  CF.sub.3                                   CH.sub.3                                       CH.sub.3    H        F  H           H  CF.sub.3                                   CH.sub.3                                       CH.sub.3    Si(CH.sub.3).sub.3             F  H           H  CF.sub.3                                   CH.sub.3                                       CH.sub.3    H        H  OCF.sub.3   H  CF.sub.3                                   H   CH.sub.3    Si(CH.sub.3).sub.3             H  OCF.sub.3   H  CF.sub.3                                   H   CH.sub.3    H        F  OCF.sub.2 CHFCl                            H  CF.sub.3                                   H   CH.sub.3    Si(CH.sub.3).sub.3             H  CO.sub.2 C.sub.2 H.sub.5                            H  CF.sub.3                                   H   CH.sub.3    H        H  CO.sub.2 C.sub.2 H.sub.5                            H  CF.sub.3                                   H   CH.sub.3    Si(CH.sub.3).sub.3             H  OCH.sub.2 CH.sub.2 CH.sub.3                            H  CF.sub.3                                   H   CH.sub.3    Si(CH.sub.3).sub.3             F  OCF.sub.3   H  CF.sub.3                                   H   CH.sub.3    Si(CH.sub.3).sub.3             F  NHCOCH.sub.3                            H  CF.sub.3                                   CH.sub.3                                       CH.sub.3    Si(CH.sub.3).sub.3             F  SCH.sub.3   H  CF.sub.3                                   H   CH.sub.3    Si(CH.sub.3).sub.3             F  SC.sub.2 H.sub.5                            H  CF.sub.3                                   H   CH.sub.3    Si(CH.sub.3).sub.3             F  S-cyclopentyl                            H  CF.sub.3                                   H   CH.sub.3    H        F  OCF.sub.3   H  CF.sub.3                                   H   CH.sub.3    H        F  NHCOCH.sub.3                            H  CF.sub.3                                   CH.sub.3                                       CH.sub.3    H        F  OCH.sub.3   H  CF.sub.3                                   H   CH.sub.3    H        F  OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                            H  CF.sub.3                                   H   CH.sub.3    H        F  OCH.sub.2 CH.sub.2 CH.sub.3                            H  CF.sub.3                                   H   CH.sub.3    H        F  OCH.sub.2 OCH.sub.3                            H  CF.sub.3                                   H   CH.sub.3    H        F  SCH.sub.3   H  CF.sub.3                                   H   CH.sub.3    H        F  SC.sub.2 H.sub.5                            H  CF.sub.3                                   H   CH.sub.3    H        F  S-cyclopentyl                            H  CF.sub.3                                   H   CH.sub.3    H        F  SCH(CH.sub.3).sub.2                            H  CF.sub.3                                   H   CH.sub.3    H        F  SCH.sub.3   H  CF.sub.3                                   CH.sub.3                                       CH.sub.3    H        F  SC.sub.2 H.sub.5                            H  CHF.sub.2                                   H   CH.sub.3    H        F  SCH.sub.2 CH.sub.2 CH.sub.3                            H  CF.sub.3                                   H   CH.sub.3    H        F  SCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                            H  CF.sub.3                                   H   CH.sub.3    H        F  SOCH.sub.3  H  CF.sub.3                                   H   CH.sub.3    H        F  SO.sub.2 CH.sub.3                            H  CF.sub.3                                   H   CH.sub.3    H        F  SO.sub.2 -cyclopentyl                            H  CF.sub.3                                   H   CH.sub.3    H        Cl SCH.sub.3   H  CF.sub.3                                   H   CH.sub.3    H        F  SO.sub.2 NH.sub.2                            H  CF.sub.3                                   H   CH.sub.3    H        F  SO.sub.2 NHCH.sub.3                            H  CF.sub.3                                   H   CH.sub.3    H        F  SO.sub.2 N(CH.sub.3).sub.2                            H  CF.sub.3                                   H   CH.sub.3    H        F  SO.sub.2 -pyrrolidin-1-yl                            H  CF.sub.3                                   H   CH.sub.3    H        F  NHSO.sub.2 CF.sub.3                            H  CF.sub.3                                   H   CH.sub.3    H        F  NHSO.sub.2 CH.sub.2 CF.sub.3                            H  CF.sub.3                                   H   CH.sub.3    H        F  N(CH.sub.3)SO.sub.2 CH.sub.3                            H  CF.sub.3                                   H   CH.sub.3    H        F  N(CH.sub.2 CH═CH.sub.2)SO.sub.2 C.sub.2 H.sub.5                            H  CF.sub.3                                   H   CH.sub.3    H        F  N(CH.sub.2 CCH)SO.sub.2 CH.sub.3                            H  CF.sub.3                                   CH.sub.3                                       CH.sub.3    H        F  N(COCH.sub.3)SO.sub.2 CH.sub.3                            H  CF.sub.3                                   H   CH.sub.3    H        F  N(COC(CH.sub.3).sub.3)SO.sub.2 CH.sub.3                            H  CF.sub.3                                   H   CH.sub.3    H        F  N(COC(CH.sub.3).sub.3)SO.sub.2 CH.sub.3                            H  CF.sub.3                                   CH.sub.3                                       CH.sub.3    H        F  NHSO.sub.2 CH.sub.3                            H  CF.sub.3                                   H   NH.sub.2    H        F  CO.sub.2 CH.sub.3                            H  CF.sub.3                                   H   CH.sub.3    H        F  CO.sub.2 C.sub.2 H.sub.5                            H  CF.sub.3                                   H   CH.sub.3    H        F  CO.sub.2 CH(CH.sub.3).sub.2                            H  CF.sub.3                                   CH.sub.3                                       CH.sub.3    H        F  CONH.sub.2  H  CF.sub.3                                   H   CH.sub.3    H        F  CON(CH.sub.3).sub.2                            H  CF.sub.3                                   H   CH.sub.3    H        F  CONHCH.sub.3                            H  CF.sub.3                                   H   CH.sub.3    H        F  CO-pyrrolidin-1-yl                            H  CF.sub.3                                   H   CH.sub.3    H        F  CONH-cyclopropyl                            H  CF.sub.3                                   H   CH.sub.3    Si(CH.sub.3).sub.3             F  5-OCH(CH.sub.3)CH.sub.2 -6                               CF.sub.3                                   H   CH.sub.3    H        F  5-OCH(CH.sub.3)CH.sub.2 -6                               CF.sub.3                                   H   CH.sub.3    Si(CH.sub.3).sub.3             F  5-OCH(CH.sub.3)CH.sub.2 -6                               CF.sub.3                                   CH.sub.3                                       CH.sub.3    H        F  5-OCH(CH.sub.3)CH.sub.2 -6                               CF.sub.3                                   CH.sub.3                                       CH.sub.3    H        F  5-OCH(CH.sub.2 OH)CH.sub.2 -6                               CF.sub.3                                   H   CH.sub.3    H        F  5-OCH(COOH)CH.sub.2 -6                               CF.sub.3                                   H   CH.sub.3    H        F  5-OCH(CO.sub.2 CH.sub.3)CH.sub.2 -6                               CF.sub.3                                   H   CH.sub.3    H        F  5-OC(CH.sub.3).sub.2 CH.sub.2 -6                               CF.sub.3                                   H   CH.sub.3    H        F  5-OC(CH.sub.3)(CH.sub.2 OH)CH-6                               CF.sub.3                                   H   CH.sub.3    H        F  5-OC(CH.sub.3)(COOH)CH.sub.2 -6                               CF.sub.3                                   H   CH.sub.3    H        F  5-OC(CH.sub.3)(CO.sub.2 C.sub.2 H.sub.5)CH.sub.2 -6                               CF.sub.3                                   H   CH.sub.3    H        F  5-OC(CH.sub.3)(CH.sub.2 OCH.sub.3)CH.sub.2 -6                               CF.sub.3                                   H   CH.sub.3    H        H  5-OCH(CH.sub.3)CH.sub.2 -6                               CF.sub.3                                   H   CH.sub.3    H        F  5-OC(CH.sub.3)═CH-6                               CF.sub.3                                   H   CH.sub.3    H        F  SO.sub.2 C.sub.2 H.sub.5                            H  CF.sub.3                                   H   CH.sub.3    Si(CH.sub.3).sub.3             F  H           H  CF.sub.3                                   H   CH.sub.3    Si(CH.sub.3).sub.3             F  NO.sub.2    H  CF.sub.3                                   H   CH.sub.3    Si(CH.sub.3).sub.3             F  N(COC(CH.sub.3).sub.3)SO.sub.2 CH.sub.3                            H  CF.sub.3                                   H   CH.sub.3    H        F  N(COC(CH.sub.3).sub.3)SO.sub.2 C.sub.2 H.sub.5                            H  CF.sub.3                                   H   CH.sub.3    H        F  N(COCH.sub.3)SO.sub.2 C.sub.2 H.sub.5                            H  CF.sub.3                                   H   CH.sub.3    Si(CH.sub.3).sub.3             F  NHSO.sub.2 C.sub.2 H.sub.5                            H  CF.sub.3                                   H   CH.sub.3    H        F  OCH.sub.2 CH(CH.sub.3)                            H  CF.sub.3                                   H   CH.sub.3    H        F  OH          H  CF.sub.3                                   H   CH.sub.3    H        F  O-cyclobutyl                            H  CF.sub.3                                   H   CH.sub.3    CH.sub.2 OH             F  OCH.sub.3   H  CF.sub.3                                   H   CH.sub.3    CH.sub.2 CH.sub.2 CH.sub.3             H  H           H  CF.sub.3                                   H   CH.sub.3    H        F  OCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                            H  CF.sub.3                                   H   CH.sub.3    H        F  OCH.sub.2 CH═CH.sub.2                            H  CF.sub.3                                   H   CH.sub.3    H        F  OCH.sub.2 C═CH                            H  CF.sub.3                                   H   CH.sub.3    H        F  OCH.sub.2 OCH.sub.3                            H  CF.sub.3                                   H   CH.sub.3    Si(CH.sub.3).sub.3             F  OCH.sub.2 OCH.sub.3                            H  CF.sub.3                                   H   CH.sub.3    Si(CH.sub.3).sub.3             F  OH          H  CF.sub.3                                   H   CH.sub.3    H        F  OCH.sub.2 C(CH.sub.3)═CH.sub.2                            H  CF.sub.3                                   H   CH.sub.3    H        F  OCH.sub.2 CH.sub.2 F                            H  CF.sub.3                                   H   CH.sub.3    H        F  OCH.sub.2 CH.sub.2 CH.sub.2 F                            H  CF.sub.3                                   H   CH.sub.3    H        F  OCH(CH.sub.3).sub.2                            H  CF.sub.3                                   H   CH.sub.3    H        F  OCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                            H  CF.sub.3                                   H   CH.sub.3    __________________________________________________________________________    3 #STR13##    R       X   Y        Zm  R.sup.2                                  R.sup.3                                       R.sup.4    __________________________________________________________________________    Si(CH.sub.3).sub.3            F   OCH.sub.3                         H   CF.sub.3                                  H    CH.sub.3    H       F   OCH.sub.3                         H   CF.sub.3                                  CH.sub.3                                       CH.sub.3    H       F   OCH(CH.sub.3).sub.2                         H   CF.sub.3                                  H    CH.sub.3    H       F   O-cyclopropyl                         H   CF.sub.3                                  H    CH.sub.3    H       F   NHSO.sub.2 CH.sub.3                         H   CF.sub.3                                  H    CH.sub.3    __________________________________________________________________________    1 #STR14##    3 #STR15##    R    X   Y         Zm  R.sup.2                                 R.sup.3                                       R.sup.4    __________________________________________________________________________    H    F   NHSO.sub.2 C.sub.2 H.sub.5                       H   CF.sub.3                                 H     CH.sub.3    H    F   NHSO.sub.2 CH.sub.3                       H   CF.sub.3                                 CH.sub.3                                       CH.sub.3    H    F   NHSO.sub.2 C.sub.2 H.sub.5                       H   CF.sub.3                                 CH.sub.3                                       CH.sub.3    H    F   CO.sub.2 CH(CH.sub.3).sub.2                       H   CF.sub.3                                 H     CH.sub.3    H    F   OCF.sub.3 H   CHF.sub.2                                 H     CH.sub.3    __________________________________________________________________________    4 #STR16##    R      X   Y        Zm  R.sup.2                                  R.sup.3                                       R.sup.5    __________________________________________________________________________    Si(CH.sub.3).sub.3           F   H        H   CF.sub.3                                  H    CH.sub.3    H      F   H        H   CF.sub.3                                  CH.sub.3                                       CH.sub.3    H      F   H        H   CHF.sub.2                                  H    CH.sub.3    H      F   H        H   CClF.sub.2                                  H    CH.sub.3    H      F   OCH.sub.3                        H   CF.sub.3                                  H    CH.sub.3    H      F   OC.sub.2 H.sub.5                        H   CF.sub.3                                  CH.sub.3                                       CH.sub.3    H      F   OCH(CH.sub.3).sub.2                        H   CF.sub.3                                  H    CH.sub.3    H      F   O-cyclopropyl                        H   CF.sub.3                                  H    CH.sub.3    H      F   NHSO.sub.2 CH.sub.3                        H   CF.sub.3                                  CH.sub.3                                       CH.sub.3    H      F   NHSO.sub.2 C.sub.2 H.sub.5                        H   CF.sub.3                                  H    CH.sub.3    H      F   CO.sub.2 CH(CH.sub.3).sub.2                        H   CF.sub.3                                  H    CH.sub.3    __________________________________________________________________________    1 #STR17##    3 #STR18##    R    X   Y           Zm  R.sup.2                                   R.sup.3                                       R.sup.5    __________________________________________________________________________    H    F   OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                         H   CF.sub.3                                   H   CH.sub.3    H    F   OCH(CH.sub.3)CO.sub.2 CH.sub.3                         H   CF.sub.3                                   H   CH.sub.3    H    F   S-cyclopropyl                         H   CF.sub.3                                   H   CH.sub.3    H    F   SCH.sub.2 CO.sub.2 CH.sub.3                         H   CF.sub.3                                   H   CH.sub.3    __________________________________________________________________________    5 #STR19##    R     X  Y        Zm R.sup.2 R.sup.3                                     R.sup.6    __________________________________________________________________________    Si(CH.sub.3).sub.3          F  H        H  CHF.sub.2                                 H   CH.sub.3    H     F  OCH.sub.3                      H  CHF.sub.2                                 Cl  CH.sub.3    H     F  OCH(CH.sub.3).sub.2                      H  CHF.sub.2                                 CH.sub.3                                     CH.sub.3    H     F  OCH(CH.sub.3).sub.2                      H  CHF.sub.2                                 H   CH.sub.3    H     F  O-cyclopropyl                      H  CHF.sub.2                                 H   CH.sub.3    H     F  OCH.sub.3                      H  CH.sub.2 CH.sub.2 CH.sub.2 F                                 H   CH(CH.sub.3).sub.2    H     F  OCH(CH.sub.3).sub.2                      H  CHF.sub.2                                 H   C.sub.2 H.sub.5    H     F  O-cyclopropyl                      H  CHF.sub.2                                 H   C(CH.sub.3).sub.3    H     F  NHSO.sub.2 CH.sub.3                      H  CHF.sub.2                                 CH.sub.3                                     CH.sub.3    H     F  NHSO.sub.2 C.sub.2 H.sub.5                      H  CHF.sub.2                                 Cl  CH.sub.3    H     F  S-cyclopentyl                      H  CHF.sub.2                                 H   CH.sub.3    H     F  OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                      H  CHF.sub.2                                 Cl  CH.sub.3    __________________________________________________________________________    1 #STR20##    6 #STR21##    R      X   Y         Zm  R.sup.3                                  R.sup.5                                       R.sup.7    __________________________________________________________________________    Si(CH.sub.3).sub.3           F   OCH.sub.3 H   H    CH.sub.3                                       CN    H      F   OCH(CH.sub.3).sub.2                         H   Cl   CF.sub.3                                       CN    H      F   O-cyclopentyl                         H   CH.sub.3                                  CHF.sub.2                                       Cl    H      F   OCH.sub.3 H   H    CF.sub.3                                       Cl    H      F   OCH(CH.sub.3).sub.2                         H   Cl   CF.sub.3                                       CF.sub.3    H      F   O-cyclopentyl                         H   CN   CF.sub.3                                       CF.sub.3    H      F   OCH(CH.sub.3).sub.2                         H   CN   H    NH.sub.2    H      F   OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                         H   CN   H    NH.sub.2    Si(CH.sub.3).sub.3           F   OCH.sub.3 H   CN   H    NH.sub.2    H      F   OCH.sub.3 H   CN   H    NH.sub.2    H      F   OC.sub.2 H.sub.5                         H   SCH.sub.3                                  H    NH.sub.2    __________________________________________________________________________    7 #STR22##    R      X  Y       Zm R.sup.5 R.sup.8                                        A.sup.1    __________________________________________________________________________    Si(CH.sub.3).sub.3           F  OCH.sub.3                      H  CHF.sub.2                                 CH.sub.3                                        O    H      F  OCH.sub.3                      H  CH.sub.2 CH.sub.2 CH.sub.2 F                                 CH.sub.3                                        O    H      F  OCH(CH.sub.3).sub.2                      H  C(CH.sub.3).sub.3                                 SCH.sub.3                                        O    H      F  O-cyclopentyl                      H  CH.sub.2 CH.sub.2 CH.sub.2 F                                 SCH(CH.sub.3).sub.2                                        O    H      F  NHSO.sub.2 CH.sub.3                      H  CH.sub.2 CH.sub.2 CH.sub.2 F                                 OCH(CH.sub.3).sub.2                                        O    H      F  OCH.sub.3                      H  CH(CH.sub.3).sub.2                                 CF.sub.3                                        S    H      F  O-cyclopentyl                      H  cyclopentyl                                 CH(CH.sub.3).sub.2                                        O    __________________________________________________________________________    1 #STR23##    7 #STR24##    R   X  Y          Zm R.sup.5 R.sup.8                                        A.sup.1    __________________________________________________________________________    H   F  CH.sub.2 CO.sub.2 C.sub.2 H.sub.5                      H  CH.sub.2 CH.sub.2 CH.sub.2 F                                 C(CH.sub.3).sub.3                                        O    H   F  NHSO.sub.2 C.sub.2 H.sub.5                      H  CH.sub.2 CH.sub.2 CH.sub.2 F                                 CH.sub.3                                        O    H   F  O-cyclopentyl                      H  CHF.sub.2                                 CH.sub.3                                        O    H   F  OCH.sub.3  H  CHF.sub.2                                 CH.sub.3                                        O    H   F  OCH(CH.sub.3).sub.2                      H  CHF.sub.2                                 CH.sub.3                                        O    H   F  CH.sub.2 CO.sub.2 C.sub.2 H.sub.5                      H  CHF.sub.2                                 CH.sub.3                                        O    H   F  OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                      H  CHF.sub.2                                 CH.sub.3                                        O    H   F  SCH(CH.sub.3)CO.sub.2 CH.sub.3                      H  CHF.sub.2                                 CH.sub.3                                        O    H   F  NHSO.sub.2 CH.sub.3                      H  CHF.sub.2                                 CH.sub.3                                        O    H   F  NHSO.sub.2 C.sub.2 H.sub.5                      H  CHF.sub.2                                 CH.sub.3                                        O    H   F  CO.sub.2 CH(CH.sub.3).sub.2                      H  CHF.sub.2                                 CH.sub.3                                        O    H   F  CH.sub.2 CHCl(CO.sub.2 C.sub.2 H.sub.5)                      H  CHF.sub.2                                 CH.sub.3                                        O    __________________________________________________________________________    8 #STR25##    R      X  Y       Zm R.sup.5 R.sup.9                                        A.sup.1    __________________________________________________________________________    Si(CH.sub.3).sub.3           F  OCH.sub.3                      H  CH.sub.2 CH.sub.2 CH.sub.2 F                                 CH.sub.3                                        O    H      F  OCH.sub.3                      H  CH.sub.2 CH.sub.2 CH.sub.2 F                                 CH(CH.sub.3).sub.2                                        O    H      F  OCH(CH.sub.3).sub.2                      H  CH.sub.2 CH.sub.2 CH.sub.2 F                                 CH.sub.3                                        O    H      F  O-cyclopentyl                      H  CH.sub.2 CH.sub.2 CH.sub.2 F                                 CH.sub.3                                        O    H      F  OCH.sub.3                      H  CHF.sub.2                                 CF.sub.3                                        O    H      F  OCH(CH.sub.3).sub.2                      H  CHF.sub.2                                 CH(CH.sub.3).sub.2                                        O    __________________________________________________________________________    1 #STR26##    8 #STR27##    R   X  Y         Zm   R.sup.5 R.sup.9                                        A.sup.1    __________________________________________________________________________    H   F  O-cyclopentyl                     H    CH.sub.2 CH.sub.2 CH.sub.2 F                                  C(CH.sub.3).sub.3                                        O    H   F  OCH(CH.sub.3).sub.2                     H    CH.sub.2 CH.sub.2 CH.sub.2 F                                  CF.sub.3                                        S    H   F  NHSO.sub.2 CH.sub.3                     H    CHF.sub.2                                  CH.sub.3                                        O    H   F  NHSO.sub.2 C.sub.2 H.sub.5                     H    CH.sub.2 CH.sub.2 CH.sub.2 F                                  CH(CH.sub.3).sub.2                                        O    H   F  CO.sub.2 CH(CH.sub.3).sub.2                     H    CHF.sub.2                                  CH.sub.3                                        O    H   F  OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                     H    CH.sub.2 CH.sub.2 CH.sub.2 F                                  C.sub.2 H.sub.5                                        O    H   F  OCH.sub.3 H    cyclopropyl                                  CF.sub.3                                        O    H   F  SCH(CH.sub.3)CO.sub.2 CH.sub.3                     H    CH.sub.2 CH.sub.2 CH.sub.2 F                                  CH.sub.3                                        O    H   H  H         3,6-Cl.sub.2                          CH.sub.3                                  CF.sub.3                                        S    H   H  H         3,6-Cl.sub.2                          CH.sub.3                                  CF.sub.3                                        O    __________________________________________________________________________    9 #STR28##    R      X   Y        Zm  R.sup.5  R.sup.9    __________________________________________________________________________    Si(CH.sub.3).sub.3           F   OCH.sub.3                        H   CHF.sub.2                                     H    H      F   OCH(CH.sub.3).sub.2                        H   CH.sub.2 CH.sub.2 CH.sub.2 F                                     CH.sub.3    H      F   O-cyclopentyl                        H   CHF.sub.2                                     CH(CH.sub.3).sub.2    H      F   OCH.sub.3                        H   CH.sub.2 CH.sub.2 CH.sub.2 F                                     C(CH.sub.3).sub.3    H      F   S-cyclopentyl                        H   CHF.sub.2                                     CH.sub.3    __________________________________________________________________________    1 #STR29##    0 #STR30##    R    X   Y           Zm  R.sup.5   R.sup.9    __________________________________________________________________________    H    F   OCH(CH.sub.3).sub.2                         H   CHF.sub.2 CH.sub.3    H    F   O-cyclopentyl                         H   CH.sub.2 CH.sub.2 CH.sub.2 F                                       CH.sub.3    H    F   NHSO.sub.2 CH.sub.3                         H   CHF.sub.2 CH.sub.3    H    F   NHSO.sub.2 C.sub.2 H.sub.5                         H   CH.sub.2 CH.sub.2 CH.sub.2 F                                       CH.sub.3    H    F   S--CH(CH.sub.3).sub.2                         H   CH.sub.2 CH.sub.2 CH.sub.2 F                                       CH.sub.3    H    F   CH.sub.2 CO.sub.2 C.sub.2 H.sub.5                         H   CH.sub.2 CH.sub.2 CH.sub.2 F                                       CH.sub.3    H    F   SCH(CH.sub.3)CO.sub.2 CH.sub.3                         H   CHF.sub.2 CHF.sub.2    __________________________________________________________________________    1 #STR31##    R      X   Y          Zm  R.sup.5  R.sup.9    __________________________________________________________________________    Si(CH.sub.3).sub.3           H   OCH.sub.3  H   CHF.sub.2                                       CH.sub.3    H      F   OCH(CH.sub.3).sub.2                          H   CH.sub.2 CH.sub.2 CH.sub.2 F                                       H    H      F   OCH(CH.sub.3).sub.2                          H   CHF.sub.2                                       H    H      F   O-cyclopentyl                          H   CH.sub.2 CH.sub.2 CH.sub.2 F                                       C.sub.2 H.sub.5    H      F   NHSO.sub.2 CH.sub.3                          H   CHF.sub.2                                       H    H      F   NHSO.sub.2 C.sub.2 H.sub.5                          H   CH.sub.2 CH.sub.2 CH.sub.2 F                                       CH.sub.3    H      F   CO.sub.2 CH(CH.sub.3).sub.2                          H   CH.sub.2 CH.sub.2 CH.sub.2 F                                       H    H      F   OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                          H   CHF.sub.2                                       H    H      F   SCH(CH.sub.3)CO.sub.2 CH.sub.3                          H   CH.sub.2 CH.sub.2 CH.sub.2 F                                       H    __________________________________________________________________________    1 #STR32##    2 #STR33##    R       X     Y           Zm    R.sup.5    __________________________________________________________________________    Si(CH.sub.3).sub.3            H     OCH(CH.sub.3).sub.2                              H     C(CH.sub.3).sub.3    H       F     OCH.sub.3   H     C(CH.sub.3).sub.3    H       F     OCH(CH.sub.3).sub.2                              H     CH(CH.sub.3).sub.2    H       F     OCH(CH.sub.3).sub.2                              H     CF.sub.3    H       F     O-cyclopentyl                              H     C(CH.sub.3).sub.3    H       F     NHSO.sub.2 C.sub.2 H.sub.5                              H     cyclopentyl    H       F     NHSO.sub.2 CH.sub.3                              H     C(CH.sub.3).sub.3    H       F     NHSO.sub.2 C.sub.2 H.sub.5                              H     C(CH.sub.3).sub.3    H       F     OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                              H     C(CH.sub.3).sub.3    Si(CH.sub.3).sub.3            F     OCH.sub.3   H     C(CH.sub.3).sub.3    __________________________________________________________________________    3 #STR34##    R        X     Y           Zm    R.sup.5    __________________________________________________________________________    Si(CH.sub.3).sub.3             H     OCH.sub.3   H     CH.sub.3    H        F     OCH(CH.sub.3).sub.2                               H     CH.sub.3    H        F     O-cyclopentyl                               H     CH(CH.sub.3).sub.2    H        F     OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                               H     CF.sub.3    H        F     NHSO.sub.2 CH.sub.3                               H     C(CH.sub.3).sub.3    H        F     NHSO.sub.2 C.sub.2 H.sub.5                               H     C(CH.sub.3).sub.3    H        F     NHSO.sub.2 CH.sub.3                               H     CH.sub.3    H        F     NHSO.sub.2 C.sub.2 H.sub.5                               H     CF.sub.3    H        F     O-cyclopentyl                               H     C(CH.sub.3).sub.3    __________________________________________________________________________    1 #STR35##    4 #STR36##    R      X  Y         Zm R.sup.5  R.sup.10                                        A.sup.1    __________________________________________________________________________    Si(CH.sub.3).sub.3           H  OCH.sub.3 H  CH.sub.3 H   O    H      F  OCH(CH.sub.3).sub.2                        H  CH.sub.3 H   O    H      F  O-cyclopentyl                        H  CH.sub.3 H   S    H      F  O-cyclopentyl                        H  CH.sub.2 CH.sub.2 CH.sub.2 F                                    H   O    H      F  OCH(CH.sub.3).sub.2                        H  CHF.sub.2                                    CH.sub.3                                        O    H      F  NHSO.sub.2 C.sub.2 H.sub.5                        H  CH.sub.2 CH.sub.2 CH.sub.2 F                                    CH.sub.3                                        O    H      F  OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                        H  CH.sub.3 H   O    H      F  NHSO.sub.2 C.sub.2 H.sub.5                        H  CH.sub.3 H   O    H      F  OCH.sub.2 OCH.sub.3                        H  CH.sub.3 H   O    H      F  OCH.sub.2 SCH.sub.3                        H  CH.sub.2 F                                    H   O    H      F  SCH.sub.2 OCH.sub.3                        H  CH.sub.3 H   O    __________________________________________________________________________    5 #STR37##    R      X  Y        Zm R.sup.5                                 R.sup.11                                        A.sup.1    __________________________________________________________________________    Si(CH.sub.3).sub.3           H  OCH.sub.3                       H  CH.sub.3                                 C(CH.sub.3).sub.3                                        O    H      F  OCH(CH.sub.3).sub.2                       H  CH.sub.3                                 cyclopropyl                                        O    H      F  O-cyclopentyl                       H  CH(CH.sub.3).sub.2                                 CF.sub.3                                        O    H      F  NHSO.sub.2 CH.sub.3                       H  CH.sub.3                                 cyclopropyl                                        S    H      F  NHSO.sub.2 C.sub.2 H.sub.5                       H  C.sub.2 H.sub.5                                 C(CH.sub.3).sub.3                                        O    H      F  NHSO.sub.2 C.sub.2 H.sub.5                       H  CH.sub.3                                 C(CH.sub.3).sub.3                                        O    __________________________________________________________________________    1 #STR38##    5 #STR39##    R   X   Y         Zm  R.sup.5                               R.sup.11 A.sup.1    __________________________________________________________________________    H   F   OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                      H   CH.sub.3                               cyclopropyl                                        O    H   F   OCH.sub.3 H   H    CH.sub.3 O    H   F   O-cyclopentyl                      H   H    cyclopropyl                                        O    __________________________________________________________________________    6 #STR40##    R    X Y      Zm                    R.sup.12                       R.sup.13    __________________________________________________________________________    Si(CH.sub.3).sub.3         F OCH.sub.3                  H Cl O-cyclopropyl    H    F OCH.sub.3                  H F  NHCH.sub.3    H    F OCH(CH.sub.3).sub.2                  H Cl NHCH.sub.3    H    F O-cyclopentyl                  H Cl NHCH.sub.3    H    F OCH.sub.3                  H Cl OCH.sub.2 CF.sub.3    H    F OCH.sub.3                  H Cl NH.sub.2    H    F OCH(CH.sub.3).sub.2                  H Cl 2,6-difluorophenyl-methoxy    H    F O-cyclopentyl                  H Cl 3-trifluoromethylpheyl-methoxy    H    F OCH.sub.3                  H Cl 5-trifluoromethylisoxazol-3-yl-methoxy    H    F O-cyclopentyl                  H Cl 4-chloro-3-trifluromethyl-1-methylpyrazole-                       4-yl-methoxy    __________________________________________________________________________    1 #STR41##    7 #STR42##    R      X   Y        Zm  R.sup.15                                   R.sup.17                                       R.sup.18    __________________________________________________________________________    Si(CH.sub.3).sub.3           H   OCH.sub.3                        H   OH     CH.sub.3                                       CH.sub.3    H      F   OCH.sub.3                        H   Cl     CH.sub.3                                       CH.sub.3    H      F   OCH(CH.sub.3).sub.2                        H   OCOCH.sub.3                                   CH.sub.3                                       CH.sub.3    H      F   O-cyclopentyl                        H   OH     CH.sub.3                                       CH.sub.3    H      F   NHSO.sub.2 CH.sub.3                        H   OH     CH.sub.3                                       CH.sub.3    H      F   NHSO.sub.2 C.sub.2 H.sub.5                        H   OH     CH.sub.3                                       CH.sub.3    __________________________________________________________________________    8 #STR43##    R       X     Y         Zm    A.sup.1                                        A.sup.2    __________________________________________________________________________    Si(CH.sub.3).sub.3            F     OCH.sub.3 H     O     O    H       F     OCH.sub.3 H     O     O    H       F     OCH(CH.sub.3).sub.2                            H     O     O    H       F     NHSO.sub.2 C.sub.2 H.sub.5                            H     O     O    H       F     O-cyclopentyl                            H     O     O    __________________________________________________________________________    1 #STR44##    9 #STR45##    R     X     Y          Zm    A.sup.1                                        A.sup.2    __________________________________________________________________________    H     F     O-cyclopentyl                           H     S      O    H     F     NHSO.sub.2 C.sub.2 H.sub.5                           H     O      O    H     F     O-cyclopentyl                           H     O      O    H     F     NHSO.sub.2 CH.sub.3                           H     S      O    __________________________________________________________________________    0 #STR46##    R          X          Y             Zm    __________________________________________________________________________    H          F          OCH.sub.3     H    __________________________________________________________________________    1 #STR47##    R      X    Y       Zm   A.sup.1                                 R.sup.19                                       R.sup.20    __________________________________________________________________________    Si(CH.sub.3).sub.3           F    OCH.sub.3                        H    O   CHF.sub.2                                       CH.sub.3    H      F    NHSO.sub.2 CH.sub.3                        H    O   CHF.sub.2                                       CH.sub.3    __________________________________________________________________________    2 #STR48##    R    X   Y     Zm  A.sup.1                           R.sup.19  R.sup.20    __________________________________________________________________________    H    F   OCH.sub.3                   H   O   CH.sub.2 CH.sub.2 CH.sub.2 F                                     CH(CH.sub.3).sub.2    __________________________________________________________________________    1 #STR49##    3 #STR50##    R    X   Y       Zm  A.sup.1                              R.sup.19                                    R.sup.20    __________________________________________________________________________    H    F   CH(CH.sub.3).sub.2                     H   O    CHF.sub.2                                    cyclopropyl    H    F   SCH.sub.3                     H   O    CH.sub.3                                    CH.sub.3    __________________________________________________________________________    4 #STR51##    R     X     Y         Zm    A.sup.1                                       R.sup.19    __________________________________________________________________________    H     F     NHSO.sub.2 CH.sub.3                          H     O      CH.sub.3    __________________________________________________________________________    5 #STR52##    R       X      Y            Zm      A.sup.1    __________________________________________________________________________    H       F      OCH(CH.sub.3).sub.2                                H       O    H       F      OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                                H       O    __________________________________________________________________________    1 #STR53##    6 #STR54##    R     X  Y          Zm R.sup.5 R.sup.10                                       R.sup.21    __________________________________________________________________________    Si(CH.sub.3).sub.3          H  OCH(CH.sub.3).sub.2                        H  CHF.sub.2                                   CH.sub.3                                       CH.sub.3    H     F  OCH.sub.3  H  CHF.sub.2                                   H   H    H     F  OCH(CH.sub.3).sub.2                        H  CH.sub.2 CH.sub.2 CH.sub.2 F                                   CH.sub.3                                       CH.sub.3    H     F  O-cyclopentyl                        H  CH.sub.3                                   CH.sub.3                                       CH.sub.3    H     F  NHSO.sub.2 CH.sub.3                        H  CHF.sub.2                                   CH.sub.3                                       CH.sub.3    H     F  NHSO.sub.2 C.sub.2 H.sub.5                        H  CH.sub.2 CH.sub.2 CH.sub.2 F                                   CH.sub.3                                       CH.sub.3    H     F  NHSO.sub.2 C.sub.2 H.sub.5                        H  CHF.sub.2                                   CH.sub.3                                       CH.sub.3    H     F  OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                        H  CHF.sub.2                                   CH.sub.3                                       CH.sub.3    H     F  OCH.sub.2 CHClCO.sub.2 C.sub.2 H.sub.5                        H  CHF.sub.2                                   CH.sub.3                                       CH.sub.3    H     F  S-cyclopentyl                        H  CHF.sub.2                                   H   H    __________________________________________________________________________    7 #STR55##    R       X    Y         Zm   R.sup.10                                       R.sup.21    __________________________________________________________________________    Si(CH.sub.3).sub.3            H    OCH.sub.3 H    H      CH.sub.3    H       F    OCH.sub.3 H    H      H    H       F    OCH.sub.3 H    CH.sub.3                                       CH.sub.3    H       F    OCH(CH.sub.3).sub.2                           H    CH.sub.3                                       CH.sub.3    H       F    O-cyclopentyl                           H    CH.sub.3                                       CH.sub.3    H       F    NHSO.sub.2 CH.sub.3                           H    CH.sub.3                                       CH.sub.3    __________________________________________________________________________    1 #STR56##    8 #STR57##    R    X    Y            Zm   R.sup.10                                       R.sup.21    __________________________________________________________________________    H    F    NHSO.sub.2 C.sub.2 H.sub.5                           H    CH.sub.3                                       CH.sub.3    H    F    OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                           H    CH.sub.3                                       CH.sub.3    H    F    OCH.sub.2 CHClCO.sub.2 C.sub.2 H.sub.5                           H    CH.sub.3                                       CH.sub.3    H    F    S-cyclopropyl                           H    CH.sub.3                                       CH.sub.3    __________________________________________________________________________    9 #STR58##    R     X  Y         Zm R.sup.15                             R.sup.10                                 R.sup.21                                     R.sup.22    __________________________________________________________________________    Si(CH.sub.3).sub.3          F  OCH.sub.3 H  H  CH.sub.3                                 CH.sub.3                                     CH(CH.sub.3).sub.2    H     F  OCH(CH.sub.3).sub.2                       H  H  CH.sub.3                                 CH.sub.3                                     CF.sub.3    H     F  O-cyclopentyl                       H  CH.sub.3                             CH.sub.3                                 CH.sub.3                                     H    H     F  OCH.sub.3 H  H  CH.sub.3                                 CH.sub.3                                     H    H     F  OCH(CH.sub.3).sub.2                       H  H  CH.sub.3                                 CH.sub.3                                     H    H     F  O-cyclopentyl                       H  H  CH.sub.3                                 CH.sub.3                                     H    H     F  NHSO.sub.2 CH.sub.3                       H  H  CH.sub.3                                 CH.sub.3                                     H    H     F  NHSO.sub.2 C.sub.2 H.sub.5                       H  H  CH.sub.3                                 CH.sub.3                                     H    H     F  OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                       H  H  CH.sub.3                                 CH.sub.3                                     H    H     F  OCH.sub.2 CHClCO.sub.2 C.sub.2 H.sub.5                       H  H  CH.sub.3                                 CH.sub.3                                     H    __________________________________________________________________________    1 #STR59##    0 #STR60##    R       X   Y            Zm  R.sup.10                                       R.sup.21    __________________________________________________________________________    Si(CH.sub.3).sub.3            H   OCH.sub.3    H   CH.sub.3                                       CH.sub.3    H       F   OCH.sub.3    H   CH.sub.3                                       CH.sub.3    H       F   OCH(CH.sub.3).sub.2                             H   CH.sub.3                                       CH.sub.3    H       F   O-cyclopentyl                             H   CH.sub.3                                       CH.sub.3    H       F   NHSO.sub.2 CH.sub.3                             H   CH.sub.3                                       CH.sub.3    H       F   NHSO.sub.2 C.sub.2 H.sub.5                             H   CH.sub.3                                       CH.sub.3    H       F   OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                             H   CH.sub.3                                       CH.sub.3    H       F   OCH.sub.2 CHClCO.sub.2 C.sub.2 H.sub.5                             H   CH.sub.3                                       CH.sub.3    H       F   S-cyclopentyl                             H   CH.sub.3                                       CH.sub.3    H       F   S-cyclopropyl                             H   CH.sub.3                                       CH.sub.3    __________________________________________________________________________    1 #STR61##    R      X  Y        Zm A.sup.1                              R.sup.5                                   R.sup.23    __________________________________________________________________________    Si(CH.sub.3).sub.3           F  OCH.sub.3                       H  O   CH.sub.2 Cl                                   Cl    H      F  OCH.sub.3                       H  O   CH.sub.2 Cl                                   Cl    H      F  OCH(CH.sub.3).sub.2                       H  O   CH.sub.2 Cl                                   Cl    H      F  O-cyclopentyl                       H  O   CH.sub.2 Cl                                   Cl    H      F  NHSO.sub.2 CH.sub.3                       H  O   CH.sub.2 Cl                                   Cl    H      F  NHSO.sub.2 C.sub.2 H.sub.5                       H  O   CH.sub.2 Cl                                   Cl    H      F  OCH.sub.3                       H  O   C.sub.2 H.sub.5                                   3-fluorophenyl    __________________________________________________________________________    0 #STR62##    1 #STR63##    R   X  Y        Zm A.sup.1                          R.sup.5                               R.sup.23    __________________________________________________________________________    H   F  OCH(CH.sub.3).sub.2                    H  O  CH.sub.2 Cl                               3,5-difluorophenyl    H   F  O-cyclopentyl                    H  O  C.sub.2 H.sub.5                               3-chlorophenyl    H   F  O-cyclopentyl                    H  O  CH.sub.2 Cl                               CONHC.sub.2 H.sub.5    H   F  OCH.sub.3                    H  O  C.sub.2 H.sub.5                               CONHC.sub.2 H.sub.5    H   F  OCH(CH.sub.3).sub.2                    H  O  C.sub.2 H.sub.5                               CONHC.sub.2 H.sub.5    H   F  O-cyclopentyl                    H  O  C.sub.2 H.sub.5                               CONHC.sub.2 H.sub.5    H   F  NHSO.sub.2 CH.sub.3                    H  O  C.sub.2 H.sub.5                               3-trifluoromethylphenyl    H   F  NHSO.sub.2 C.sub.2 H.sub.5                    H  O  C.sub.2 H.sub.5                               3-fluorophenyl    H   F  OCH(CH.sub.3).sub.2                    H  S  C.sub.2 H.sub.5                               3-fluorophenyl    H   F  O-cyclopentyl                    H  S  C.sub.2 H.sub.5                               3,5-difluorophenyl    __________________________________________________________________________    2 #STR64##    R    X  Y        Zm R.sup.24      R.sup.25    __________________________________________________________________________    Si(CH.sub.3).sub.3         H  OCH.sub.3                     H  phenyl        CONH.sub.2    H    F  OCH.sub.3                     H  2-fluorophenyl                                      CONH.sub.2    H    F  OCH(CH.sub.3).sub.2                     H  phenyl        CONH.sub.2    H    F  O-cyclopentyl                     H  2,6-difluorophenyl                                      CONH.sub.2    H    F  NHSO.sub.2 CH.sub.3                     H  3-fluorophenyl                                      CONH.sub.2    H    F  NHSO.sub.2 C.sub.2 H.sub.5                     H  fluorophenyl  CONH.sub.2    H    F  OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                     H  2-trifluorophenylmethylphenyl                                      CONH.sub.2    H    F  S-cyclopentyl                     H  2,4-difluorophenyl                                      CONH.sub.2    __________________________________________________________________________    1 #STR65##    3 #STR66##    R      X  Y        Zm A.sup.1                              A.sup.2                                 R.sup.26    __________________________________________________________________________    Si(CH.sub.3).sub.3           F  OCH.sub.3                       H  O   O  C(CH.sub.3).sub.3    H      F  OCH.sub.3                       H  O   O  C(CH.sub.3).sub.3    H      F  OCH(CH.sub.3).sub.2                       H  O   O  C(CH.sub.3).sub.3    H      F  O-cyclopentyl                       H  O   O  C(CH.sub.3).sub.3    H      F  OCH.sub.3                       H  O   O  1-acetyl-cyclopentyl    H      F  OCH(CH.sub.3).sub.2                       H  O   O  1-cyanoisopropyl    H      F  O-cyclopentyl                       H  O   O  1-cyanocylohexyl    H      F  NHSO.sub.2 CH.sub.3                       H  O   O  1-methylcyclohexyl    H      F  NHSO.sub.2 C.sub.2 H.sub.5                       H  O   O  C(CH.sub.3).sub.3    H      F  O-cyclopentyl                       H  O   O  CH.sub.2 CH.sub.2 CH.sub.2 F    __________________________________________________________________________    3 #STR67##    R  X   Y         Zm  A.sup.1                             A.sup.3                                 R.sup.26    __________________________________________________________________________    H  F   OCH(CH.sub.3).sub.2                     H   S   O   C(CH.sub.3).sub.3    H  F   O-cyclopentyl                     H   S   O   1-cyano-cyclopropyl    H  F   OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                     H   S   O   1-methylcyclopropyl    __________________________________________________________________________    1 #STR68##    4 #STR69##    R   X  Y        Zm A.sup.1                           A.sup.2                               R.sup.26    __________________________________________________________________________    H   F  OCH(CH.sub.3).sub.2                    H  O   CH.sub.2                               1,1-dimethyl-2-propynyl    H   F  NHSO.sub.2 C.sub.2 H.sub.5                    H  S   CH.sub.2                               1,1-dimethyl-2-propynyl    H   F  O-cyclopentyl                    H  O   CH.sub.2                               C(CH.sub.3).sub.3    __________________________________________________________________________    5 #STR70##    R       X     Y          Zm    R.sup.5    __________________________________________________________________________    Si(CH.sub.3).sub.3            F     OCH.sub.3  H     CH.sub.3    H       F     OCH.sub.3  H     CHF.sub.2    H       F     OCH(CH.sub.3).sub.2                             H     CHF.sub.2    H       F     O-cyclopentyl                             H     CHF.sub.2    H       F     OCH(CH.sub.3).sub.2                             H     CH.sub.2 CH.sub.2 CH.sub.2 F    H       F     NHSO.sub.2 CH.sub.3                             H     CHF.sub.2    H       F     NHSO.sub.2 C.sub.2 H.sub.5                             H     CHF.sub.2    H       F     NHSO.sub.2 C.sub.2 H.sub.5                             H     CH.sub.2 CH.sub.2 CH.sub.2 F    H       F     OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                             H     CHF.sub.2    H       F     S-cyclopentyl                             H     CHF.sub.2    H       H     OCF.sub.3  H     CHF.sub.2    H       F     OCH(CH.sub.3).sub.2                             H     cyclopropyl    H       F     O-cyclopentyl                             H     C(CH.sub.3).sub.3    H       F     OCHF.sub.2 H     CHF.sub.2    __________________________________________________________________________    1 #STR71##    6 #STR72##    R      X   Y        Zm  A.sup.1                                R.sup.5                                    R.sup.27    __________________________________________________________________________    Si(CH.sub.3).sub.3           F   OCH.sub.3                        H   O   CH.sub.3                                    CH.sub.3    H      F   OCH(CH.sub.3).sub.2                        H   O   C.sub.2 H.sub.5                                    CF.sub.3    H      F   O-cyclopentyl                        H   O   C.sub.2 H.sub.5                                    CF.sub.3    H      F   OCH.sub.3                        H   S   C.sub.2 H.sub.5                                    CF.sub.3    H      F   OCH(CH.sub.3).sub.2                        H   S   C.sub.2 H.sub.5                                    cyclopropyl    H      F   O-cyclopentyl                        H   S   CH.sub.3                                    CF.sub.3    H      F   NHSO.sub.2 CH.sub.3                        H   O   C.sub.2 H.sub.5                                    CF.sub.3    H      F   NHSO.sub.2 CH.sub.3                        H   S   C.sub.2 H.sub.5                                    CF.sub.3    H      F   OCH(CH.sub.3).sub.2                        H   O   C.sub.2 H.sub.5                                    OCH.sub.2 CF.sub.3    H      F   OCH.sub.3                        H   O   C.sub.2 H.sub.5                                    C(CH.sub.3).sub.3    __________________________________________________________________________    7 #STR73##    R          X           Y            Zm    __________________________________________________________________________    H          F           OC.sub.2 H.sub.5                                        H    __________________________________________________________________________    8 #STR74##    R     X     Y         Zm    R.sup.10                                       R.sup.10    __________________________________________________________________________    H     F     OCH(CH.sub.3).sub.2                          H     CH.sub.3                                       CH.sub.3    __________________________________________________________________________    1 #STR75##    9 #STR76##    R     X      Y       Zm     R.sup.10                                       R.sup.10    __________________________________________________________________________    H     F      OCH.sub.3                         H      CH.sub.3                                       CH.sub.3    __________________________________________________________________________    0 #STR77##    R   X    Y         Zm   A.sup.1                                 R.sup.10                                       R.sup.28    __________________________________________________________________________    H   F    O-cyclopropyl                       H    O    H     H    H   F    OC.sub.2 H.sub.5                       H    O    Cl    H    __________________________________________________________________________    1 #STR78##    R       X       Y           Zm      A.sup.1    __________________________________________________________________________    H       F       OCH(CH.sub.3).sub.2                                H       O    __________________________________________________________________________    2 #STR79##    R      X       Y            Zm      A.sup.1    __________________________________________________________________________    H      F       OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                                H       O    H      F       OCH.sub.3    H       O    __________________________________________________________________________

When in the process (a), for example3-(4-bromo-5-ethoxy-2-fluorophenyl)-1-methyl-6-trifluoro-methyl-2,4(1H,3H)-pyrimidinedioneand trimethylsilylacetylene are used as the starting materials, thecourse of the reaction can be represented by the following equation:##STR80##

When in the process (b), for example3-(5-ethoxy-2-fluoro-4-{2-(trimethylsilyl)-1-ethynyl}phenyl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione is desilylated by potassium fluoride, the course ofthe raction can be represented by the following equation: ##STR81##

The first starting materials used in the process (a) according to theinvention are those as definied by formula (II) above.

In the process (a) according to the invention, the starting materials ofthe formula (II) mean based on the above definitions of X, Y, Z, m, Qand hal, prefearbly substituents based on the above preferreddefinitions of X, Y, Z, m and Q.

The above process (a) can be conducted according to Tetrahedron Letters1975, 4467. The compounds of the formula (II) used as the startingmaterial are known compounds which are described in the above-mentionedprior art literatures, or they can be synthesized by the same processesas described in the above-mentioned prior art literatures.

Examples of the compounds of the formula (II) are as follows:

3-(4-bromophenyl)-1-methyl-6-trifluoromethyl-2,4 (1H,3H)-pyrimidinedione,

3-(4-iodophenyl)-1-methyl-6-trifluoromethyl-2,4 (1H,3H)-pyrimidinedione,

3-(4-bromo-2-fluorophenyl)-1-methyl-6-trifluoromethyl-2,4 (1H,3H)-pyrimidinedione,

3-(4-bromo-2-fluoro-5-methoxyphenyl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-(4-bromo-5-ethoxy-2-fluorophenyl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)pyrimidinedione,

3-(4-bromo-2-fluoro-5-propoxyphenyl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-(4-bromo-2-fluoro-5-isopropoxyphenyl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-(4-bromo-5-cyclopropoxy-2-fluorophenyl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-(4-bromo-5-cyclopentyloxy-2-fluorophenyl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-(4-bromo-2-fluoro-5-methoxymethoxyphenyl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-(4-bromo-2-fluoro-5-methoxycarbonylmethoxyphenyl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-(4-bromo-5-ethoxycarbonylmethoxy-2-fluorophenyl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-(4-bromo-5-isopropoxy-2-fluorophenyl)-1,5-dimethyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-(4-bromo-2-fluoro-5-methylthiophenyl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-(4-bromo-5-ethylthio-2-fluorophenyl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-(4-bromo-2-fluoro-5-propylthiophenyl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-(4-bromo-2-fluoro-5-isopropylthiophenyl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-(4-bromo-5-cyclopropylthio-2-fluorophenyl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-(4-bromo-5-cyclopentylthio-2-fluorophenyl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-(4-bromo-2-fluoro-5-methoxymethylthiophenyl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-(4-bromo-2-fluoro-5-methoxycarbonylmethylthiophenyl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-(4-bromo-5-ethoxycarbonylmethylthio-2-fluorophenyl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-(4-bromo-2-fluoro-5-methylsulfonylphenyl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-(4-bromo-5-ethylsulfonyl-2-fluorophenyl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-(4-bromo-5-cyclopentylsulfonyl-2-fluorophenyl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-(4-bromo-2-fluoro-5-methylsulfinylphenyl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-(4-bromo-5-ethylsulfinyl-2-fluorophenyl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-(4-bromo-5-cyclopentylsulfinyl-2-fluorophenyl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-(4-bromo-2-fluoro-5-nitrophenyl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-(4-bromo-2-fluoro-5-nitrophenyl)-1,5-dimethyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

methyl 2-bromo-5-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidinyl!-4-fluorobenzoate,

ethyl 2-bromo-5-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyimidinyl!-4-fluorobenzoate,

isopropyl 2-bromo-5-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidinyl!-4-fluoro-benzoate,

isopropyl 2-bromo-5-3,6-dihydro-2,6-dioxo-3,5-dimethyl-4-trifluoromethyl-1(2H)pyrimidinyl!-4-fluorobenzoate,

3-(7-bromo-5-fluoro-2-methyl-2,3-dihydrobenzob!furan-4-yl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-(7-bromo-5-fluoro-2-hydroxymethyl-2,3-dihydrobenzob!furan-4-yl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-(7-bromo-5-fluoro-2-methoxymethyl-2,3-dihydro-benzob!furan-4-yl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione,

methyl 7-bromo-4-3,6-dihydro-2,6-dioxo-3,5-dimethyl-4-trifluoromethyl-1(2H)-pyrimidinyl!-5-fluoro-2,3-dihydrobenzob!furan-2-carboxylate,

3-(7-bromo-5-fluoro-2,2-dimethyl-2,3-dihydro-benzob!furan-4-yl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,.

3-(7-bromo-5-fluoro-2-hydroxymethyl-2-ethyl-2,3-dihydrobenzob!furan-4-yl)-1-methyl-6-trifluoro-methyl-2,4(1H, 3H)-pyrimidinedione,

3-(7-bromo-5-fluoro-2-methoxymethyl-2-methyl-2,3-dihydrobenzob!furan-4-yl)-1-methyl-6-trifluoro-methyl-2,4(1H, 3H)-pyrimidinedione,

methyl 7-bromo-5-fluoro-2-methyl-4-3,6-dihydro-2,6-dioxo-3,5-dimethyl-4-trifluoromethyl-1(2H)-pyrimidinyl!-2,3-dihydrobenzob!furan-2-carboxylate,

3-(7-bromo-5-fluoro-2-methylbenzob!furan-4-yl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

1-(4-bromo-2-fluoro-5-methoxyphenyl)-4-(3-fluoropropyl)-4,5-dihydro-1H-1,2,3,4-tetrazol-5-one,

1-(4-bromo-2-fluoro-5-nitrophenyl)-4-(3-fluoropropyl)-4,5-dihydro-1H-1,2,3,4-tetrazol-5-one,

1-(4-bromo-2-fluoro-5-methoxyphenyl)-4-difluoromethyl-4,5-dihydro-1H-1,2,3,4-tetrazol-5-one,

1-(4-bromo-2-fluoro-5-nitrophenyl)-4-difluoromethyl-4,5-dihydro-1H-1,2,3,4-tetrazol-5-one,

3-(4-bromo-2-fluorophenyl)-4-chloro-5-difluoromethoxy-1-methyl-1H-pyrazole,

3-(4-bromo-2-fluoro-5-methoxyphenyl)-4-chloro-5-difluoromethoxy-1-methyl-1H-pyrazole,

3-(4-bromo-2-fluoro-5-nitrophenyl)-4-chloro-5-difluoromethoxy-1-methyl-1H-pyrazole,

1-(4-bromo-2-fluoro-5-methoxyphenyl)-4-difluoromethyl-3-methyl-4,5-dihydro-1H-1,2,4-triazol-5-one,

1-(4-bromo-2-fluoro-5-nitrophenyl)-4-difluoromethyl-3-methyl-4,5-dihydro-1H-1,2,4-triazol-5-one,

2-(4-bromo-2-fluoro-5-methoxyphenyl)-4-methyl-2,3,4,5-tetrahydro-1,2,4-triazin-3,5-dione,

N-(4-bromo-2-fluoro-5-methoxyphenyl)-3,4,5,6-tetrahydrophthalimide,

N-(4-bromo-2-fluoro-5-isopropoxyphenyl)-3,4,5,6-tetrahydrophthalimide,

N-(4-bromo-2-fluoro-5-nitrophenyl)-3,4,5,6-tetrahydrophthalimide,

2-(4-bromo-2-fluoro-5-methoxyphenyl)perhydro- 1,2,4!triazolo1,2-a!pyridazin-1,3-dione,

3-(4-bromo-2-fluoro-5-isopropoxyphenylimino)-5,6-dihydro-6,6-dimethyl-3H-thiazolo2,3-C! 1,2,4!thiaziazole,

3-(4-bromo-2-fluoro-5-methoxyphenylimino)-6,7-dihydro-6,6-dimethyl-3H,5H-pyrrolo2,1-C! 1,2,4!thiaziazole, and the like.

The second starting materials used in the process (a) according to theinvention are those as defined by formula (III) above.

The compounds of the formula (III) used as the starting material of theprocess (a) are well known in the field of organic chemistry andexamples thereof include trimethyl-silylacetylene,3,3-dimethyl-1-butyne, propyne, 1-hexyne, ethynylbenzene, and the like.

The starting materials used in the process (b) according to theinvention are those as defined by formula (Ia) above.

In the process (b), the compounds of the formula (Ia) used as thestarting material are those which can be synthesized by the aboveprocess (a), and constitute a part of the compounds of the invention.

Examples of the compounds of the formula (Ia) are as follows:

3-{4-2-(trimethylsilyl)-1-ethynyl!phenyl}-1-methyl-6-trifluoromethyl-2,4(1,3H)-pyrimidinedione,

3-{2-fluoro-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-{2-fluoro-5-methoxy-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-1-methyl-6-trifluoromethyl-2,4(1,3H)-pyrimidinedione,

3-{5-ethoxy-2-fluoro-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-{2-fluoro-5-propoxy-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-{2-fluoro-5-isopropoxy-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-1-methyl-6trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-{5-cyclopropoxy-2-fluoro-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-{5-cyclopentyloxy-2-fluoro-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-{2-fluoro-5-methoxymethoxy-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-{2-fluoro-5-methoxycarbonylmethoxy-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-{5-ethoxycarbonylmethoxy-2-fluoro-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-{2-fluoro-5-isopropoxy-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-1,5-dimethyl-6trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-{2-fluoro-5-methylthio-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-{5-ethylthio-2-fluoro-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-{2-fluoro-5-propylthio-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-{2-fluoro-5-isopropylthio-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-{5-cyclopropylthio-2-fluoro-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-{5-cyclopentylthio-2-fluoro-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-{2-fluoro-5-methoxymethylthio-4-2-(trimethylsilyl)-1-ethyhyl!phenyl}-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-{2-fluoro-5-methoxycarbonylmethylthio-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-{5-ethoxycarbonylmethylthio-2-fluoro-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-1-methyl-6-trifluoromethyl-2,4(1H,-3H)-pyrimidinedione,

3-{2-fluoro-5-methylsulfonyl-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,.

3-{5-ethylsulfonyl-2-fluoro-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-{5-cyclopentylsulfonyl-2-fluoro-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-{2-fluoro-5-methylsulfinyl-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-{5-ethylsulfinyl-2-fluoro-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-{5-cyclopentylsulfinyl-2-fluoro-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-{5-amino-2-fluoro-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-{5-amino-2-fluoro-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-1,5-dimethyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

methyl 5-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidinyl!-4-fluoro-2-2-(trimethylsilyl)1-ethynyl!benzoate,

ethyl 5-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidinyl!-4-fluoro-2-2-(trimethylsilyl)-1-ethynyl!benzoate,

isopropyl 5-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidinyl!-4-fluoro-2-2-(trimethylsilyl)-1-ethynyl!benzoate,

isopropyl 5-3,6-dihydro-2,6-dioxo-3,5-dimethyl-4-trifluoromethyl-1(2H)-pyrimidinyl!-4-fluoro-2-2-(trimethylsilyl)-1-ethynyl!benzoate,

3-{5-fluoro-2-methyl-7- 2-(trimethylsilyl)-1-ethynyl!-2,3-dihydrobenzob!furan-4-yl}-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-{5-fluoro-2-hydroxymethyl-7-2-(trimethylsilyl)-1-ethynyl!-2,3-dihydrobenzob!furan-4-yl}-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-{5-fluoro-2-methoxymethyl-7-2-(trimethylsilyl)-1-ethynyl!-2,3-dihydrobenzob!furan-4-yl)-1-methyl-6-trifluoromethyl-2,4(1,3H)-pyrimidinedione,

methyl 4-3,6-dihydro-2,6-dioxo-3,5-dimethyl-4-trifluoromethyl-1(2H)-pyrimidinyl!-5-fluoro-7-2-(trimethylsilyl)-1-ethynyl!-2,3-dihydrobenzo b!furan-2-carboxylate,

3-{5-fluoro-2,2-dimethyl-7-2-(trimethylsilyl)-1-ethynyl!-2,3-dihydrobenzob!furan-4-yl}-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-{5-fluoro-2-hydroxymethyl-2-methyl-7-2-(trimethylsilyl)-1-ethynyl!-2,3-dihydrobenzob!furan-4-yl}-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

3-{5-fluoro-2-methoxymethyl-2-methyl-7-2-(trimethylsilyl)-1-ethynyl!-2,3-dihydrobenzob!furan-4-yl}-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,

methyl 4-3,6-dihydro-2,6-dioxo-3,5-dimethyl-4-trifluoromethyl-1(2H)-pyrimidinyl!-5-fluoro-2-methyl-7-2-(trimethylsilyl)-1-ethynyl!-2,3-dihydrobenzo b!furan-2-carboxylate,

3-{5-fluoro-2-methyl-7- 2-(trimethylsilyl)-1-ethynyl!-benzob!furan-4-yl}-1-methyl-6-trifluoro-methyl-2,4(1H,3H)-pyrimidinedione,

1-{2-fluoro-5-methoxy-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-4-(3-fluoropropyl)-4,5-dihydro-1H-1,2,3,4-tetrazol-5-one,

1-{2-fluoro-5-nitro-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-4-(3-fluoropropyl)-4,5-dihydro-1H-1,2,3,4-tetrazol-5-one,

1-difluoromethyl-4-{2-fluoro-5-methoxy-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-4,5dihydro-1H-1,2,3,4-tetrazol-5-one,

1-difluoromethyl-4-{2-fluoro-5-nitro-4-2-(trimethylsilyl)-1-ethynyl!phenyl)-4,5dihydro-1H-1,2,3,4-tetrazol-5-one,

4-chloro-5-difluoromethoxy-3-{2-fluoro-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-1-methyl-1H-pyrazole,

4-chloro-5-difluoromethoxy-3-{2-fluoro-5-methoxy-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-1-methyl-1H-pyrazole,

4-chloro-5-difluoromethoxy-3-{2-fluoro-5-nitro-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-1-methyl-1H-pyrazole,

4-difluoromethyl-1-{2-fluoro-5-methoxy-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-3-methyl-4,5-dihydro-1H-1,2,4-triazol-5-one,

4-difluoromethyl-1-{2-fluoro-5-nitro-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-3-methyl-4,5-dihydro-1H-1,2,4-triazol-5-one,

2-{2-fluoro-5-methoxy-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-4-methyl-2,3,4,5-tetrahydro-1,2,4-triazine-3,5-dione,

N-{2-fluoro-5-methoxy-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-3,4,5,6-tetrahydrophthalimide,

N-{2-fluoro-5-isopropoxy-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-3,4,5,6-tetrahydrophthalimide,

N-{2-fluoro-5-nitro-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-3,4,5,6-tetrahydrophthalimide,

2-{2-fluoro-5-methoxy-4- 2-(trimethylsilyl)-1-ethynyl!phenyl}perhydro1,2,4!triazolo 1,2-a!pyridazine-1,3-dione,

3-{2-fluoro-5-methoxy-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-5,6-dihydro-6,6-dimethyl-3H-thiazolo2,3-C! 1,2,4!thiadiazole,

3-(2-fluoro-5-methoxy-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-6,7-dihydro-6,6-dimethyl-3H,5H-pyrrolo2,1-C! 1,2,4!thiadiazole, and the like.

Examples of desilylating agents used in the above process (b) includepotassium fluoride, tetrabutylammonium fluoride, sodiumhydrogencarbonate, potassium hydrogencarbonate, sodium carbonate,potassium carbonate, sodium hydroxide, potassium hydroxide, lithiumhydroxide, calcium hydroxide, and the like.

The reaction of the above process (a) can be carried out in the presenceof inert solvents. Examples of usable solvents are: aliphatic, alicyclicor aromatic hydrocarbons (which may optionally be chlorinated) such aspentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, tolueneand xylene; ethers such as ethyl ether, methyl ethyl ether, isopropylether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran(TTh) and diethylene glycol dimethyl ether (DGM); nitriles such asacetonitrile, propionitrile and acrylonitrile; acid amides such asdimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone,1,3-dimethyl-2-imidazolidinone and hexamethylphosphoric triamide (HMPA);and bases such as pyridine, diethylamine, diisopropylamine, piperidine,pyrrolidine, triethylamine and tributylanine.

The reaction of the process (a) can be carried out in the presence of anacid binder. Examples of usable acid binding agents, which may bementioned, are: inorganic bases, for example, carbonates andbicarbonates of alkali metals or alkaline earth metals, such as sodiumhydrogencarbonate, potassium hydrogencarbonate, sodium carbonate andpotassium carbonate; organic bases, for example, tertiary amines,dialkylaminoanilines and pyridines, such as triethylamine,tributylamine, 1,1,4,4-tetramethylethylenediamine (TMEDA),N,N-dimethylaniline, N,N-diethylaniline, pyridine,4-dimethylaminopyridine (DMAP), 1,4-diazabicyclo 2,2,2!octane (DABCO)and 1,8-diazabicyclo 5,4,0!undec-7-ene (DBU); organic lithium compounds,such as methyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyllithium, phenyllithium, dimethyl copper lithium, lithiumdiisopropylamide, lithium cyclohexylisopropylamide, lithiumdicyclohexylamide, n-butyl lithium-DABCO, n-butyl lithium-DBU andn-butyl lithium-TMEDA.

The reaction of the process (a) is preferably conducted in the presenceof a palladium catalyst and a promotor. Examples of the palladiumcatalysts include dichlorobis(triphenylphosphine)palladium,tetrakistriphenylphosphine palladium, palladiumchloride-triphenylphosphine, palladium acetate-triphenylphosphine, andthe like. Further, examples of the promoters include, for example,copper(I) iodide.

The reaction of the process (a) can be conducted at a temperature withina substantially broad range, but it is preferred to carry out a reactionat a temperature of about -80 to about 150° C., preferably about 0 toabout 120° C. Further, the reaction should preferably be conducted undernormal pressure but it may optionally be operated under elevated orreduced pressure.

For carrying out the process (a), for instance, 1 mole of the compoundof the formula (II) can be reacted with 1 to 5 molar amounts of thecompound of the formula (III) in a solvent such as tetrahydrofuran inthe presence of a palladium catalyst (0.005 to 0.2 molar amount),copper(I) chloride (0.005 to 0.2 molar amount) and an acid binding agent(1 to 5 molar amounts) to thereby obtain the objective compound of theformula (I).

The reaction of the above process (b) can also be carried out in thepresence of appropriate inert solvents. Examples of usable solvents are:water; aliphatic, alicyclic or aromatic hydrocarbons (which mayoptionally be chlorinated) such as pentane, hexane, cyclohexane,petroleum ether, ligroin, benzene, toluene, xylene, dichloromethane,chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene anddichloro-benzene; ethers such as ethyl ether, methyl ethyl ether,isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME),tetrahydrofuran (THF) and diethylene glycol dimethyl ether (DGM);ketones such as acetone, methyl ethyl ketone (MEK), methylisopropylketone and methyl isobutylketone (MIBK); nitrites such as acetonitrile,propionitrile and acrylonitrile; alcohols such as methanol, ethanol,isopropanol, butanol and ethylene glycol; esters such as ethyl acetateand amyl acetate; acid amides such as dimethylformamide (DMF),dimethylacetamide (DMA), N-methylpyrrolidone,1,3-dimethyl-2-imidazolidinone and hexamethylphosphoric triamide (HMPA);sulfones and sulfoxides such as dimethyl sulfoxide (DMSO) and sulforan;and bases such as pyridine.

The reaction of the process (b) can be conducted at a temperature withina substantially broad range, but it is preferred to carry out a reactionat a temperature of about -80 to about 150° C., preferably about -20 toabout 120° C. Further, the reaction should preferably be conducted undernormal pressure but it may optionally be operated under elevated orreduced pressure.

For carrying out the process (b), for instance, 1 mole of the compoundof the formula (Ia) can be reacted with 1 to 3 molar amounts of adesilylating agent in a diluent such as ethanol to thereby obtain theobjective compound of formula (I).

The compounds of formula (I) according to the invention can also besynthesized by processes which are different from the above processes(a) and (b).

Specific explanations are given hereafter considering for example a caseof producing the compounds of the formula (I) wherein Q is aheterocyclic group represented by the formula: ##STR82##

The respective compounds of formula (I) can be synthesized by thefollowing process:

(c) in the case where R³ is chlorine:

compounds of the formula (IV) ##STR83## wherein R, R², R⁶, X, Y, Z and mare defined as above, are reacted with chlorine gas or sulfurylchloride, if appropriate, in the presence of inert solvents, or

(d) in the case where R² is C₁₋₆ haloallyl and R³ is hydrogen:

compounds of the formula (V) ##STR84## wherein R, R⁶, X Y, Z and m aredefined as above, are reacted with halides of the formula (VI)

    hal--R.sup.2                                               (VI)

wherein hal and R² are defined as above, in the presence of inertsolvents and, if approproate, in the presence of an acid binder, or

(e) in the case where R² and R³ represent hydrogen:

compounds of the formula (VII) ##STR85## wherein R, X, Y, Z and m aredefined as above, and R²⁹ is methyl or ethyl, are reacted with compoundsof the formula (VIII)

    R.sup.6 --NH--NH.sub.2                                     (VIII)

wherein R⁶ is defined as above, in the presence of inert solvents.

In the above process (c), the compounds of formula (IV) used as thestarting material are included in the compounds of formula (I) accordingto the invention, and can be synthesized, for example, by the aboveprocess (d). The chlorination of the compounds of formula (IV) by use ofchlorine gas or sulfonyl chloride can be carried out by the methodswhich are well known in the field of organic chemistry.

In the above process (d), the compounds of formula (V) used as thestarting material are included in the compounds of formula (I) accordingto the invention, and can be synthesized, for example, by the aboveprocess (e).

In the process (d), the compounds of formula (VI) used as the startingmaterial are well known in the field of organic chemistry.

The reaction of the compounds of formula (V) with the halide of formula(VI) according to the process (d) can be carried out by the methodswhich are well known in the field of organic chemistry.

In the above process (e), the compounds of the formula (VII) used as thestarting material are as follows:

methyl 3-{2-fluoro-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-3-oxopropionate,

ethyl 3-{2-fluoro-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-3-oxopropionate,

methyl 3- -4-(1-ethynyl)-2-fluorophenyl!-3-oxopropionate,

ethyl 3- -4-(1-ethynyl)-2-fluorophenyl!-3-oxopropionate,

methyl 3-{5-cyanomethoxy-2-fluoro-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-3-oxopropionate,

ethyl 3-{5-cyanomethoxy-2-fluoro-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-3-oxopropionate,

methyl 3- 5-cyanomethoxy-4-(1-ethynyl)-2-fluorophenyl}-3-oxopropionate,

ethyl 3- 5-cyanomethoxy-4-(1-ethynyl)-2-fluorophenyl}-3-oxopropionate,

methyl 3-{5-aminocarbonylmethoxy-2-fluoro-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-3-oxopropionate,

ethyl 3-{5-aminocarbonylmethoxy-2-fluoro-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-3-oxopropionate,

methyl 3-5-aminocarbonylmethoxy-4-(1-ethynyl)-2-fluorophenyl!-3-oxopropionate,

ethyl 3-5-aminocarbonylmethoxy-4-(1-ethynyl)-2-fluorophenyl!-3-oxopropionate,

methyl 3-{2-fluoro-5-methoxy-4-2-trimethylsilyl)-1-ethynyl!phenyl}-3-oxopropionate,

ethyl 3-{2-fluoro-5-methoxy-4-2-trimethylsilyl)-1-ethynyl!phenyl}-3-oxopropionate,

methyl 3- 4-(1-ethynyl)-2-fluoro-5-methoxyphenyl!-3-oxopropionate,

ethyl 3- 4-(1-ethynyl)-2-fluoro-5-methoxyphenyl!-3-oxopropionate, andthe like.

In the above process (e), the compounds of formula (VII) used as astarting material can be obtained, for instance, by the followingprocesses:

(f) in the case where R is another group than hydrogen:

compounds of the formula (IX) ##STR86## wherein R²⁹, hal, X, Y, Z and mare defined as above, are reacted with the compound of the above formula(III), in the presence of inert solvents, an acid binder, a catalyst anda promotor, or

(g) in the case where R is hydrogen:

compounds of the formula (X) ##STR87## wherein R²⁹, X, Y, Z and m aredefined as above are desilylated in the presence of inert solvents.

The reaction of the above process (f) can be conducted under the sameconditions as those of the process (a) mentioned above. Examples of thecompounds of the formula (IX) as the starting material are:

methyl 3-(4-bromo-2-fluorophenyl)-3-oxopropionate,

ethyl 3-(4-bromo-2-fluorophenyl)-3-oxopropionate,

methyl 3-(4-bromo-5-cyanomethoxy-2-fluorophenyl)-3-oxopropionate,

ethyl 3-(4-bromo-5-cyanomethoxy-2-fluorophenyl)-3-oxopropionate,

methyl3-(5-aminocarbonylmethoxy-4-bromo-2-fluorophenyl)-3-oxopropionate,

ethyl 3-(5-aminocarbonylmethoxy-4-bromo-2-fluorophenyl)-3-oxopropionate,

methyl 3-(4-bromo-2-fluoro-5-methoxyphenyl)-3-oxopropionate,

ethyl 3-(4-bromo-2-fluoro-5-methoxyphenyl)-3-oxopropionate, and thelike.

The compounds of the formula (IX) can be synthesized, for instance, bythe following processes:

(h) compounds of the formula (XI) ##STR88## wherein hal, X, Y, Z and mare defined as above, are reacted with compound of the formula:##STR89## in the presence of inert solvents and acid binder, or

(i) compounds of the formula (XIII) ##STR90## wherein hal, X, Y, Z and mare defined as above, are reacted with compounds of the formula (XIV)##STR91## wherein R²⁹ is defined as above, in the presence of inertsolvents and if appropriate in the presence of an acid binder.

Both processes (h) and (i) are well known in the field of organicchemistry, and the compounds of formulae (XI) to (XIV) used as thestarting materials are known in the field of organic chemistry.

Examples of the compounds of formula (XI) include4-bromo-2-fluorobenzoyl chloride, 4-bromo-5-cyanomethoxy-2-fluorobenzoylchloride, 5-aminocarbonylmethoxy-4-bromo-2-fluorobenzoyl chloride,4-bromo-2-fluoro-5-methoxybenzoyl chloride, and the like.

Examples of the compounds of formula (XIII) include1-(4-bromo-2-fluorophenyl)-1-ethanone,1-(4-bromo-5-cyanomethoxy-2-fluorophenyl)-1-ethanone,1-(5-aminocarbsonylmethoxy-4-bromo-2-fluorophenyl)-1-ethanone,1-(4-bromo-2-fluoro-5methoxyphenyl)-1-ethanone, and the like.

The reaction of the above process (g) can be conducted under the sameconditions as those of the process (b) mentioned above. Examples of thecompounds of formula (X) used as the starting material include,

methyl 3-{2-fluoro-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-3-oxopropionate,

ethyl 3-{2-fluoro-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-3-oxopropionate,

methyl 3-{5-cyanomethoxy-2-fluoro-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-3-oxopropionate,

ethyl 3-{5-cyanomethoxy-2-fluoro-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-3-oxopropionate,

methyl 3-{5-aninocarbonylmethoxy-2-fluoro-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-3-oxopropionate,

ethyl 3-{5-aminocarbonylmethoxy-2-fluoro-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-3-oxopropionate,

methyl 3-{2-fluoro-5-methoxy -4-2-(trimethylsilyl)-1-ethynyl!phenyl}-3-oxopropionate,

ethyl 3-{2-fluoro-5-methoxy-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-3-oxopropionate, and the like.

In the above process (g), the compounds of formula (X) used as thestarting material can be produced by the above process (f).

The active compounds according to the invention can be used asdefoliants, desiccants, agents for destroying broad-leaved plants and,especially, as weedkillers.

By weeds, in the broadest sense, there are to be understood all plantswhich grow in locations where they are undesired. Whether the substancesaccording to the invention act as total or selective herbicides dependsessentially on the amount used.

The active compounds according to the invention can be used, forexample, in connection with the following plants:

Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria,Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio,Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum,Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala,Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis,Papaver and Centaurea.

Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus,Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana,Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.

Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum,Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus,Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis,Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea,Dactyloctenium, Agrostis, Alopecurus and Apera.

Monocotyledon cultures of the genera: Oryza, Zea, Triticum, Hordeum,Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus andAllium.

However, the use of the active compounds according to the invention isin no way restricted to these genera, but also extends in the samemanner to other plants.

The compounds are suitable, depending on the concentration, for thetotal combating of weeds, for example on industrial terrain and railtracks, and on paths and squares with or without tree plantings.Equally, the compounds can be employed for combating weeds in perennialcultures, for example afforestations, decorative tree plantings,orchards, vineyards, citrus groves, nut orchards, banana plantations,coffee plantations, tea plantations, rubber plantations, oil palmplantations, cocoa plantations, soft fruit plantings and hopfields, andfor the selective combating of weeds in annual cultures.

The active compounds can be converted into the customary formulations,such as solutions, emulsions, wettable powders, suspensions, powders,foams, pastes, granules, tablets, aerosols, natural and syntheticmaterials impregnated with active compound, very fine capsules inpolymeric substances, coating compositions for use on seed, andformulations used with burning equipment, such as fumigating cartridges,fumigating cans and fumigating coils, as well as ULV cold mist and warmmist formulations.

These formulations may be produced in known manner, for example bymixing the active compounds with extenders, that is to say liquid orliquefied gaseous or solid diluents or carriers, optionally with the useof surface-active agents, that is to say emulsifying agents and/ordispersing agents and/or foam-forming agents. In the case of the use ofwater as an extender, organic solvents can, for example, also be used asauxiliary solvents.

As liquid solvents diluents or carriers, there are suitable in the main,aromatic hydrocarbons, such as xylene, toluene or alkyl napthalenes,chlorinated aromatic or chlorinated aliphatic hydrocarbons, such aschloro-benzene, chloroethylenes or methylene chloride, aliphatichydrocarbons, such as cyclohexane or paraffins, for example mineral oilfractions, alcohols, such as butanol or glycol as well as their ethersand esters, ketones, such as acetone, methyl ethyl ketone,methyl-isobutyl ketone or cyclohexanone, or strongly polar solvents,such as dimethylformamide and dimethyl-sulphoxide, as well as water.

By liquefied gaseous diluents or carriers are meant liquids which wouldbe gaseous at normal temperature and under normal pressure, for exampleaerosol propellants, such as halogenated hydrocarbons as well as butane,propane, nitrogen and carbon dioxide.

As solid carriers there may be used ground natural minerals, such askaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite ordiatomaceous earth, and ground synthetic minerals, such ashighly-dispersed silicic acid, alumina and silicates. As solid carriersfor granules there may be used crushed and fractionated natural rockssuch as calcite, marble, pumice, sepiolite and dolomite, as well assynthetic granules of inorganic and organic meals, and granules oforganic material such as sawdust, coconut shells, maize cobs and tobaccostalks.

As emulsifying and/or foam-forming agents there may be used non-ionicand anionic emulsifiers, such as polyoxyethylene-fatty acid esters,polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycolethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well asalbumin hydrolysis products.

Dispersing agents include, for example, lignin sulphite waste liquorsand methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or lattices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, can be used in theformulation.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dye stuffs, azo dye stuffs or metal phthalocyanine dyestuffs, and trace nutrients, such as salts of iron, manganese boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain from 0.1 to 95 per cent by weight ofactive compound, preferably from 0.5 to 90 percent by weight.

The active compounds according to the invention, as such or in the formof their formulations, can also be used, for combating weeds, asmixtures with known herbicides, finished formulations or tank mixesbeing possible.

Mixtures with other known active compounds, such as herbicides,fungicides, insecticides, acaricide, nematicide, bird repellents, plantnutrients and agents which improve soil structure, are also possible.

The active compounds can be used as such, in the form of theirformulations or in the use forms prepared therefrom by further dilution,such as ready-to-use solutions, suspensions, emulsions, powders, pastesand granules. They are used in the customary manner, for example bywatering, spraying, atomizing or scattering.

The active compounds according to the invention can be applied eitherbefore or after emergence of the plants.

They can also be incorporated into the soil before sowing. They areused, in particular, after emergence of the plants.

The amount of active compound used can vary within a substantial range.It depends essentially on the nature of the desired effect. In general,the amounts used are between 0.001 and 5 kg of active compound perhectare of soil surface, preferably between 0.01 and 2 kg per ha.

The preparation and use of the active compounds according to theinvention can be seen from the following examples.

SYNTHESIS EXAMPLE 1 ##STR92## 3-{5-Ethoxy-2-fluoro-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-1-methyl-6-trifluoromethyl-2,4(1H-,3H)-pyrimidinedione(1.37 g) was dissolved in ethanol (14 ml). To this solution, an aqueoussolution (1 ml) of potassium fluoride (0.30 g) was added dropwise atroom temperature and the mixture was stirred for further 8 hours. Afterthe reaction, ethanol was distilled off under reduced pressure,extracted with ethyl acetate, washed with water, and then dried overanhydrous magnesium sulfate. Then, ethyl acetate was distilled off andthe resulting oily substance was purified by chromatography on silicagel (ethyl acetate: n-hexane=1:3) to obtain the objective 3-5-ethoxy-4-(1-ethynyl)-2-fluorophenyl!-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione(0.94 g).

melting point: 139.5-140.5° C.

Synthesis Example 2 ##STR93##3-(4-Bromo-5-ethoxy-2-fluorophenyl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione(1.59 g), trimethylsilylacetylene (0.76 g), a palladiumchloride-ditri-phenylphosphine complex (136 mg) and copper(I) iodide (35mg) were suspended in triethylamine (15 ml), and the mixture was stirredat 50° C. for 5 hours. After the reaction, triethylamine was distilledoff under reduced pressure. Then, ethyl acetate was added thereto andinsolubles were filtered. Ethyl acetate was distilled off and theresulting residue was purified by chromatography on silica gel (ethylacetate: n-hexane=1:3 v/v) to obtain the objective3-{5-ethoxy-2-fluoro-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione(1.48 g).

melting point: 98-101° C.

Synthesis Example 3 ##STR94## N-{5-3,6-dihydro-2,6-dioxo-3,5-dimethyl-4-trifluoromethyl-1(2H)-pyrimidinyl!-4-fluoro-2-2-(trimethylsilyl)-1-ethynyl!phenyl}methanesulfonamide (0.84 g) wasdissolved in ethanol (7.5 ml). To this solution, an aqueous solution(0.6 ml) of potassium fluoride (0.16 g) was added dropwise, and themixture was stirred for further 8 hours. After the reaction, ethanol wasdistilled off under reduced pressure, extracted with ethyl acetate,washed with water, and then dried over anhydrous magnesium sulfate.Ethyl acetate was distilled off and the resulting oily substance waspurified by chromato-graphy on silica gel (ethyl acetate : n-hexane=1:3v/v) to obtain the objective N-{5-3,6-dihydro-2,6-dioxo-3,5-dimethyl-4-trifluoromethyl-1(2H)-pyrimidinyl!-2-(1-ethynyl)-4-fluorophenyl}methane-sulfonamide(0.40 g).

melting point: 207-208° C.

Synthesis Example 4 ##STR95## 3-{5-Amino-2-fluoro-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-1,5-dimethyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione(2.07 g) was dissolved in pyridine (25 ml). To this solution,methanesulfonyl chloride (0.63 g) was added dropwise at 0° C. in such amanner that the inner temperature did not exceed 10° C., and the mixturewas stirred at room temperature for further 12 hours. After thereaction, pyridine was distilled off under reduced pressure, extractedwith methylene chloride, washed with diluted hydrochloric acid andwater, and then dried over anhydrous magnesium sulfate. Methylenechloride was distilled off to obtain crude crystals (2.53 g) of theobjective N-{5-3,6-dihydro-2,6-dioxo-3,5-dimethyl-4-trifluoromethyl-1(2H)-pyrimidinyl!-4-fluoro-2-2-(trimethylsilyl)-1-ethynyl!phenyl}-methanesulfonamide. Without beingpurified, this was used for the reaction of Synthesis Example 3.Synthesis Example 5 ##STR96## 3-{5-Fluoro-2-methyl-7-2-(trimethylsilyl)-1-ethynyl!-2,3-dihydrobenzob!furan-4-yl}-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione(0.39 g) was dissolved in ethanol (4 ml). To this solution, an aqueoussolution (0.3 ml) of potassium fluoride (84 mg) was added dropwise atroom temperature, and the mixture was stirred for further 8 hours. Afterthe reaction, ethanol was distilled off under reduced pressure,extracted with ethyl acetate, washed with water, and then dried overanhydrous magnesium sulfate. Ethyl acetate was distilled off and theresulting oily substance was purified by chromatography on silica gel(ethyl acetate: n-hexane=1:3 v/v) to obtain the objective 3-7-(1-ethynyl)-5-fluoro-2-methyl-2,3-dihydrobenzob!furan-4-yl!-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione(0.26 g).

melting point: 69-72.5° C.

Synthesis Example 6 ##STR97##3-(7-Bromo-5-fluoro-2-methyl-2,3-dihydrobenzob!furan-4-yl)-1-methyl-6-trifluoromethyl-2,4(1-3H)-pyrimidinedione (1.15g), trimethylsilylacetylene (0.53 g), a palladiumchloride-ditriphenylphospline complex (95 mg) and copper(I) iodide (27mg) was suspended in triethylamine (11 ml) and DMF (3 ml), and themixture was stirred at 50° C. for 12 hours. After the reaction,triethylamine was distilled off under reduced pressure. Ethyl acetatewas added thereto, and the insolubles were filtered. Then, ethyl acetatewas distilled off, and the resulting residue was purified bychromatography on silica gel (ethyl acetate: n-hexane=1:3 v/v) to obtainthe objective 3-{5-fluoro-2-methyl-7-2-(trimethylsilyl)-1-ethynyl!-2,3-dihydrobenzob!furan-4-yl}-1-methyl-6-trifluoromethyl-2,4(1H,-3H)-pyrimidinedione(0.40 g).

Table 2 shows the compounds obtained in the above Synthesis Examples 1to 6, together with the compounds obtained in the same way as theSynthesis Examples 1 to 6.

                                      TABLE 2    __________________________________________________________________________     ##STR98##                            2 #STR99##    Compound                           melting point (°C.) or    No.    R     X   Y   Zn  R.sup.2   refractive index (n.sub.D.sup.20)    __________________________________________________________________________     1     H     F   H   H   CH.sub.2 CH.sub.2 CH.sub.2 F                                       92-93     2     Si(CH.sub.3).sub.3                 F   H   H   CH.sub.2 CH.sub.2 CH.sub.2 F                                       1.545    __________________________________________________________________________    3 #STR100##    Compound                           melting point (°C.) or    No.   R    X  Y        Zn R.sup.2                                 R.sup.3                                    R.sup.4                                       refractive index (n.sub.D.sup.20)    __________________________________________________________________________     3    H    F  OCH.sub.3                           H  CF.sub.3                                 CH.sub.3                                    CH.sub.3                                       65-68     4    H    F  O-cyclopentyl                           H  CF.sub.3                                 H  CH.sub.3                                         155-155.5     5    H    H  H        H  CF.sub.3                                 H  CH.sub.3                                       176-177     6    H    F  NHSO.sub.2 CH.sub.3                           H  CF.sub.3                                 CH.sub.3                                    CH.sub.3                                       207-208     7    H    F  5-OCH(CH.sub.3)CH.sub.2 -6                              CF.sub.3                                 H  CH.sub.3                                         68-72.5     8    H    F  OCH.sub.3                           H  CF.sub.3                                 H  CH.sub.3                                       59-61     9    Si(CH.sub.3).sub.3               H  H        H  CF.sub.3                                 H  CH.sub.3                                       182.5-194    10    Si(CH.sub.3).sub.3               F  O-cyclopentyl                           H  CF.sub.3                                 H  CH.sub.3                                       140-142    11    Si(CH.sub.3).sub.3               F  OC.sub.2 H.sub.5                           H  CF.sub.3                                 H  CH.sub.3                                        98-101    12    H    F  OC.sub.2 H.sub.5                           H  CF.sub.3                                 H  CH.sub.3                                       139.5-140.5    13    H    Cl H        H  CF.sub.3                                 H  CH.sub.3                                         151-152.5    14    C(CH.sub.3).sub.3               Cl H        H  CF.sub.3                                 H  CH.sub.3                                       118.5-119.5    __________________________________________________________________________     ##STR101##                            3 #STR102##    Compound                           melting point (°C.) or    No.   R       X  Y      Zn                              R.sup.2                                 R.sup.3                                    R.sup.4                                       refractive index (n.sub.D.sup.20)    __________________________________________________________________________    15    CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                  Cl H      H CF.sub.3                                 H  CH.sub.3                                       1.545    16    C(CH.sub.3).sub.3                  Cl H      H CF.sub.3                                 H  CH.sub.3                                         141-142.5    17    H       F  NHSO.sub.2 CH.sub.3                            H CF.sub.3                                 H  CH.sub.3                                         69-71.5    18    H       F  OSO.sub.2 CH.sub.3                            H CF.sub.3                                 H  CH.sub.3                                       206-207    19    H       F  N(SO.sub.2 CH.sub.3).sub.2                            H CF.sub.3                                 H  CH.sub.3                                       255.5-256.5    20    H       F  NO.sub.2                            H CF.sub.3                                 H  CH.sub.3                                       191-192    21    H       F  OCH(CH.sub.3).sub.2                            H CF.sub.3                                 CH.sub.3                                    CH.sub.3                                         125-126.5    22    Si(CH.sub.3).sub.3                  F  NO.sub.2                            H CF.sub.3                                 CH.sub.3                                    CH.sub.3                                       152-154    23    H       F  NO.sub.2                            H CF.sub.3                                 CH.sub.3                                    CH.sub.3                                       66-68    24    Si(CH.sub.3).sub.3                  F  NH.sub.2                            H CF.sub.3                                 CH.sub.3                                    CH.sub.3                                       192-198    25    H       F  NH.sub.2                            H CF.sub.3                                 CH.sub.3                                    CH.sub.3                                       179-182    26    H       F  H      H CF.sub.3                                 CH.sub.3                                    CH.sub.3                                       154.5-155    27    Si(CH.sub.3).sub.3                  F  H      H CF.sub.3                                 CH.sub.3                                    CH.sub.3                                       131.5-132.5    28    H       H  OCF.sub.3                            H CF.sub.3                                 H  CH.sub.3                                       124-125    29    Si(CH.sub.3).sub.3                  H  OCF.sub.3                            H CF.sub.3                                 H  CH.sub.3                                       96-98    30    H       F  OCF.sub.2 CHFCl                            H CF.sub.3                                 H  CH.sub.3                                       1.5068    31    Si(CH.sub.3).sub.3                  H  CO.sub.2 C.sub.2 H.sub.5                            H CF.sub.3                                 H  CH.sub.3                                       139    32    H       H  CO.sub.2 C.sub.2 H.sub.5                            H CF.sub.3                                 H  CH.sub.3                                       126-127    33    Si(CH.sub.3).sub.3                  H  OCH.sub.2 CH.sub.2 CH.sub.3                            H CF.sub.3                                 H  CH.sub.3                                       63-65    34    Si(CH.sub.3).sub.3                  F  OCF.sub.3                            H CF.sub.3                                 H  CH.sub.3                                       1.4969    35    Si(CH.sub.3).sub.3                  F  NHCOCH.sub.3                            H CF.sub.3                                 CH.sub.3                                    CH.sub.3                                       89-96    36    H       F  OCF.sub.3                            H CF.sub.3                                 H  CH.sub.3                                       1.5075    37    H       F  NHCOCH.sub.3                            H CF.sub.3                                 CH.sub.3                                    CH.sub.3                                       230-231    38    H       F  OCH.sub.2 CH.sub.2 CH.sub.3                            H CF.sub.3                                 H  CH.sub.3                                       120-122    __________________________________________________________________________    4 #STR103##    Compound                           melting point (°C.) or    No.   R     X  Y    Zn R.sup.3                               R.sup.5                                  R.sup.7                                       refractive index (n.sub.D.sup.20)    __________________________________________________________________________    39    Si(CH.sub.3).sub.3                F  OCH.sub.3                        H  CN  H  NH.sub.2                                       172-173    40    H     F  OCH.sub.3                        H  CN  H  NH.sub.2                                       250 or more    __________________________________________________________________________    5 #STR104##    Compound                           melting point (°C.) or    No.    R     X   Y     Zn  R.sup.5 refractive index (n.sub.D.sup.20)    __________________________________________________________________________    41     H     F   OCH.sub.3                           H   C(CH.sub.3).sub.3                                       226    42     Si(CH.sub.3).sub.3                 F   OCH.sub.3                           H   C(CH.sub.3).sub.3                                       1.5372    __________________________________________________________________________     ##STR105##                            6 #STR106##    Compound                           melting point (°C.) or    No.   R     X  Y       Zn R.sup.2  refractive index (n.sub.D.sup.20)    __________________________________________________________________________    43    H     F  N(SO.sub.2 C.sub.2 H.sub.5).sub.2                           H  CH.sub.2 CH.sub.2 CH.sub.2 F                                       143-148    44    Si(CH.sub.3).sub.3                F  N(SO.sub.2 C.sub.2 H.sub.5).sub.2                           H  CH.sub.2 CH.sub.2 CH.sub.2 F                                       42-45    45    Si(CH.sub.3).sub.3                F  NH.sub.2                           H  CH.sub.2 CH.sub.2 CH.sub.2 F                                       112-113    46    Si(CH.sub.3).sub.3                F  NO.sub.2                           H  CH.sub.2 CH.sub.2 CH.sub.2 F                                       85-90    47    H     F  NHSO.sub.2 C.sub.2 H.sub.5                           H  CH.sub.2 CH.sub.2 CH.sub.2 F                                       1.5752    __________________________________________________________________________    7 #STR107##    Compound                           melting point (°C.) or    No.   R    X Y          Zn                              R.sup.2                                 R.sup.3                                    R.sup.4                                       refractive index (n.sub.D.sup.20)    __________________________________________________________________________    48    H    F SO.sub.2 CH.sub.3 CH.sub.3                            H CF.sub.3                                 H  CH.sub.3                                       208    49    Si(CH.sub.3).sub.3               F H          H CF.sub.3                                 H  CH.sub.3                                       136-138    50    Si(CH.sub.3).sub.3               F NO.sub.2   H CF.sub.3                                 H  CH.sub.3                                       161-165    51    Si(CH.sub.3).sub.3               F N(COC(CH.sub.3).sub.3)SO.sub.2 CH.sub.3                            H CF.sub.3                                 H  CH.sub.3                                       225-227    52    H    F N(COC(CH.sub.3).sub.3)SO2C.sub.2 H.sub.5                            H CF.sub.3                                 H  CH.sub.3                                       197-199    53    H    F N(COCH.sub.3)SO2C.sub.2 H.sub.5                            H CF.sub.3                                 H  CH.sub.3                                       72-77    54    Si(CH.sub.3).sub.3               F NHSO.sub.2 CH.sub.2 CH.sub.3                            H CF.sub.3                                 H  CH.sub.3                                       171-172    55    H    F OCH.sub.2 CH(CH.sub.3).sub.2                            H CF.sub.3                                 H  CH.sub.3                                       48-57    56    H    F OH         H CF.sub.3                                 H  CH.sub.3                                       86-90    57    H    F O-cyclobutyl                            H CF.sub.3                                 H  CH.sub.3                                       56-66    58    CH.sub.2 OH               F OCH.sub.3  H CF.sub.3                                 H  CH.sub.3                                       73-79    __________________________________________________________________________     ##STR108##                            7 #STR109##    Compound                           melting point (°C.) or    No.   R    X Y          Zn                              R.sup.2                                 R.sup.3                                    R.sup.4                                       refractive index (n.sub.D.sup.20)    __________________________________________________________________________    59    H    F OCH.sub.2 CH═CH.sub.2                            H CF.sub.3                                 H  CH.sub.3                                       103-104    60    H    F OCH.sub.2 C═CH                            H CF.sub.3                                 H  CH.sub.3                                       56-59    61    H    F OCH.sub.2 OCH.sub.3                            H CF.sub.3                                 H  CH.sub.3                                       49-56    62    Si(CH.sub.3).sub.3               F OCH.sub.2 OCH.sub.3                            H CF.sub.3                                 H  CH.sub.3                                       72-77    63    Si(CH.sub.3).sub.3               F OH         H CF.sub.3                                 H  CH.sub.3                                       81-86    64    H    F OCH.sub.2 C(CH.sub.3)═CH.sub.2                            H CF.sub.3                                 H  CH.sub.3                                       102-105    65    H    F OCH.sub.2 CH.sub.2 F                            H CF.sub.3                                 H  CH.sub.3                                       62-66    66    H    F OCH.sub.2 CH.sub.2 CH.sub.2 F                            H CF.sub.3                                 H  CH.sub.3                                       75-79    67    H    F OCH(CH.sub.3).sub.2                            H CF.sub.3                                 H  CH.sub.3                                       68-80    68    H    F OCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                            H CF.sub.3                                 H  CH.sub.3                                       1.5328    69    H    F H          H CF.sub.3                                 H  CH.sub.3                                       149-151    70    H    F N(COC(CH.sub.3).sub.3)SO.sub.2 CH.sub.3                            H CF.sub.3                                 CH.sub.3                                    CH.sub.3                                       235-236    71    H    F NHSO.sub.2 CH.sub.2 CH.sub.3                            H CF.sub.3                                 H  CH.sub.3                                       78-85    72    H    F SCH.sub.3  H CF.sub.3                                 H  CH.sub.3                                       136-138    73    H    F S-cyclopentyl                            H CF.sub.3                                 H  CH.sub.3                                       122-125    74    Si(CH.sub.3).sub.3               F SCH.sub.3  H CF.sub.3                                 H  CH.sub.3                                       64-70    75    Si(CH.sub.3).sub.3               F S-cyclopentyl                            H CF.sub.3                                 H  CH.sub.3                                       48-54    76    H    F OCH.sub.2 CO.sub.2 CH.sub.3                            H CF.sub.3                                 H  CH.sub.3                                       139-140    77    Si(CH.sub.3).sub.3               F OCH.sub.2 CO.sub.2 CH.sub.3                            H CF.sub.3                                 H  CH.sub.3                                       55-63    78    H    F SO.sub.2 -cyclopentyl                            H CF.sub.3                                 H  CH.sub.3                                       175-177    79    H    F SCH.sub.2 CH.sub.3                            H CF.sub.3                                 H  CH.sub.3                                       91-93    80    Si(CH.sub.3).sub.3               F SCH.sub.2 CH.sub.3                            H CF.sub.3                                 H  CH.sub.3                                       1.5513    __________________________________________________________________________

SYNTHESES OF INTERMEDIATES Synthesis Example 7 (Synthesis of thestarting material for Synthesis Example 2) ##STR110##3-(4-Bromo-5-ethoxy-2-fluorophenyl)-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione(2.38 g), methyl iodide (1.06 g) and potassium carbonate (1.04 g) weresuspended in DMF (12 ml), and the mixture was stirred at roomtemperature for about 8 hours. After the reaction, DMF was distilled offunder reduced pressure, extracted with ethyl acetate, washed with water,and dried over anhydrous magnesium sulfate. Then, ethyl acetate wasdistilled off, and the resulting residue was crystallized from a mixedsolvent of ethyl acetate and n-hexane (1:5 v/v) to obtain the objective3-(4-bromo-5-ethoxy-2-fluorophenyl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione(2.08 g).

melting point: 127-127.5° C.

Synthesis Example 8 (Synthesis of the starting material for SynthesisExample 7) ##STR111## Ethyl 3-amino-4,4,4-trifluorocrotonate (3.42 g)was dissolved in DMF (19 ml). To this solution, a suspension of sodiummethoxide (1.10 g) in DMF was added dropwise at 5° C., and the mixturewas stirred at 5° C. for 30 minutes. Then, a DMF solution of ethylN-(4-bromo-5-ethoxy-2-fluorophenyl)-carbamate was added dropwisethereto, and the mixture was stirred at 130° C. for 4 hours. After thereaction, DMF was distilled off under reduced pressure. Then, theresidue was acidified by adding diluted hydrochloric acid thereto. Thiswas extracted with ethyl acetate, washed with water, and dried overanhydrous magnesium sulfate. Then, ethyl acetate was distilled off, andthe resulting residue was crystallized from a mixed solvent of ethylacetate and n-hexane (1:3 v/v) to obtain the objective3-(4-bromo-5-ethoxy-2-fluorophenyl)-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione(3.63 g).

melting point: 161-162.5 ° C.

Synthesis Example 9 (Synthesis of the starting material for SynthesisExample 8) ##STR112## Ethyl chloroformate (2.15 g) was added dropwise toa solution of 4-bromo-5-ethoxy-2-fluoroaniline (4.21 g) and pyridine(2.84 g) in methylene chloride (36 ml) at 0° C., and the mixture wasstirred at 10° C. for 3 hours. After the reaction, this was extractedwith methylene chloride, then washed with diluted hydrochloric acid andan aqueous sodium hydrogencarbonate solution, and dried over anhydrousmagnesium sulfate. Then, methylene chloride was distilled off, and theresulting crude crystals were crystallized from a mixed solvent of ethylacetate and n-hexane (1:5 v/v) to obtain the objective ethylN-(4-bromo-5-ethoxy-2-fluorophenyl)carbamate (5.30 g).

melting point: 92.5-95° C.

Synthesis Example 10 (Synthesis of the starting material for SynthesisExample 9) ##STR113## 5-Amino-2-bromo-4-fluorophenol (10.30 g), ethyliodide (9.36 g) and potassium carbonate (7.59 g) were suspended inacetonitrile (100 ml), and the mixture was heated under refluxing forabout 6 hours. After the reaction, the precipitates were filtered, thesolvent was distilled off, extracted with ethyl acetate, and dried overanhydrous magnesium sulfate. Then, ethyl acetate was distilled off, andthe resulting oily substance was purified by chromatography on silicagel (ethyl acetate n-hexane=1:3 v/v) to obtain the objective4-bromo-5-ethoxy-2-fluoroaniline (7.93 g). n_(D) ²⁰ =1.3579 SynthesisExample 11 (Synthesis of the starting material for Synthesis Example 4)##STR114##

A mixture consisting of 3-{2-fluoro-5-nitro-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-1,5-dimethyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione(11.95 g), iron powder (15.68 g), acetic acid (14 ml), water (14 ml) andethanol (280 ml) was heated to 80° C. and stirred for 3 hours. Then, thesolvent was distilled off under reduced pressure. An aqueous sodiumhydroxide solution was added thereto to make it alkaline. Then,methylene chloride was added thereto for extraction. After washing withwater, it was dried over anhydrous magnesium sulfate. Then, methylenechloride was distilled off, and the resulting residue was crystallizedfrom a mixed solvent of ethyl acetate and n-hexane (1:3 v/v) to obtain3-{5-amino-2-fluoro-4-2-(trimethylsilyl)-1-ethynyl!-phenyl}-1,5-dimethyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione(7.70 g).

melting point: 192-198° C.

Synthesis Example 12 (Synthesis of the starting material for SynthesisExample 11) ##STR115##3-(4-Bromo-2-fluoro-5-nitrophenyl)-1,5-dimethyl-6-trifluoromethyl-2,4(1H,3H)pyrimidinedione (12.85 g), trimethylsilylacetylene (5.93 g), a palladiumchloride-ditriphenylphosphine complex (1.06 g) and copper(I) iodide(0.302 g) were suspended in triethylamine (210 ml), and the mixture wasstirred at room temperature for 5 hours. After the reaction,triethylamine was distilled off under reduced pressure. Ethyl acetatewas added thereto, and insolubles were filtered. Then, ethyl acetate wasdistilled off, and the resulting residue was purified by chromatographyon silica gel (ethyl acetate : n-hexane=1:3) to obtain the objective3-{2-fluoro-5-nitro-4-2-(trimethylsilyl)-1-ethynyl!phenyl}-1,5-dimethyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione(11.63 g).

melting point: 152-154° C.

Synthesis Example 13 (Synthesis of the starting material for SynthesisExample 12) ##STR116##3-(4-Bromo-2-fluorophenyl)-1,5-dimethyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione(14.79 g) was dissolved in concentrated sulfuric acid (190 ml). To thissolution, fuming nitric acid (2.69 g) was added dropwise at 0° C. insuch a manner that the inner temperature did not exceed 10° C., and themixture was stirred 10° C. for further 5 hours.

The reaction mixture was poured into ice water, and extracted withmethylene chloride. After washing with water, it was dried overanhydrous magnesium sulfate. Then, methylene chloride was distilled offto obtain the objective3-(4-bromo-2-fluoro-5-nitrophenyl)-1,5-dimethyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione(16.44 g). Without being purified, this was used for a subsequentreaction.

Synthesis Example 14 (Synthesis of the Starting Material for SynthesisExample 13) ##STR117##3-(4-Bromo-2-fluorophenyl)-S-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione(16.52 g), methyl iodide (7.99 g) and potassium carbonate (7.76 g) weresuspended in DMF (90 ml), and the mixture was stirred at roomtemperature for about 8 hours. After the reaction, DMF was distilled offunder reduced pressure, extracted with ethyl acetate, washed with water,and dried over anhydrous magnesium sulfate. Ethyl acetate was distilledoff, and the resulting residue was crystallized from a mixed solvent ofethyl acetate and n-hexane (1:3 v/v) to obtain the objective3-(4-bromo-2-fluoro-phenyl)-1,5-dimethyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione(14.92 g).

melting point: 129-131° C.

Synthesis Example 15 (Synthesis of the starting material for SynthesisExample 14) ##STR118## Ethyl 3-amino-4,4,4-trifluoro-2-methylcrotonate(26.0 g) was dissolved in DMF (123 ml). To this solution, a suspensionof sodium methoxide in DMF (7.78 g) was added dropwise at 0° C., and themixture was stirred at 5° C. for 30 minutes. Then, a DMF solution ofethyl N-(4-bromo-2-fluoro-phenyl)carbamate (31.44 g) was added dropwisethereto, and the mixture was stirred at 130° C. for 5 hours. After thereaction, DMF was distilled off under reduced pressure, and the residuewas acidified by adding diluted hydrochloric acid thereto. This wasextracted with ethyl acetate, washed with water, and then dried overanhydrous magnesium sulfate. Ethyl acetate was distilled off, and theresulting residue was crystallized from ethyl acetate--n-hexane (1:3v/v) to obtain the objective3-(4-bromo-2-fluorophenyl)-5-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione(18.78 g).

melting point: 187.5-189° C.

Synthesis Example 16 (Synthesis of the starting material for SynthesisExample 15) ##STR119## Ethyl chloroformate (15.91 g) was added dropwiseto a solution of 4-bromo-2-fluoroaniline (25.33 g) and pyridine (21.06g) in methylene chloride (260 ml) at 0° C., and the mixture was stirredat 10° C. for 3 hours. After the reaction, it was extracted withmethylene chloride, then washed with diluted hydrochloric acid and anaqueous sodium hydrogencarbonate solution, and dried over anhydrousmagnesium sulfate. Then, methylene chloride was distilled off, and theresulting crude crystals were crystallized from ethyl acetate--n-hexane(1:5 v/v) to obtain the objective ethylN-(4-bromo-2-fluorophenyl)carbamate (34.45 g).

melting point: 72-73° C.

Synthesis Example 17 (Synthesis of the starting material for SynthesisExample 6) ##STR120##3-(2-Allyl-4-bromo-6-fluoro-3-hydroxyphenyl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidine-dione(1.50 g) was dissolved in xylene (15 ml). After p-toluenesulfonic acidmonohydrate (0.54 g) was added thereto, it was allowed to react underthe refluxing condition for 12 hours. After the completion of thereaction, it was extracted with ethyl acetate, washed with an aqueoussodium hydrogencarbonate solution and water, and then dried overanhydrous magnesium sulfate. Ethyl acetate was distilled off, and theresulting oily substance was purified by chromatography on silica gel(ethyl acetate:n-hexane=1:3) to obtain the objective3-(7-bromo-5-fluoro-2-methyl-2,3-dihydro-benzob!furan-4-yl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione(1.46 g).

melting point: 66-75.5° C.

Synthesis Example 18 (Synthesis of the starting material for SynthesisExample 17) ##STR121##3-(5-Allyloxy-4-bromo-2-fluorophenyl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione(3.17 g) was dissolved in N, N-diethylaniline (11 ml) and allowed toreact at 210° C. for 2.5 hours. After the completion of the reaction,the reaction solution was poured into water, and diluted hydrochloricacid was added thereto for acidification. It was extracted with ethylacetate, washed with water, and then dried over anhydrous magnesiumsulfate. Ethyl acetate was distilled off, and the resulting oilysubstance was purified by chromatography on silica gel (ethyl acetate :n-hexane=1:2 v/v) to obtain the objective3-(2-allyl-4-bromo-6-fluoro-3-hydroxyphenyl)-1-methyl-6-trifluor-omethyl-2,4(1H,3H)-pyrimidinedione(2.57 g).

n_(D) ²⁰ =1.5491

Synthesis Example 19 (Synthesis of the starting material for SynthesisExample 18) ##STR122## A crude product (16.67 g) of3-(5-allyloxy-4-bromo-2-fluorophenyl)-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione,methyl iodide (7.18 g) and potassium carbonate (7.03 g) were suspendedin DMF (80 ml), and the mixture was stirred at room temperature for 8hours. After the reaction, DMF was distilled off under reduced pressure,extracted with ethyl acetate, washed with water, and dried overanhydrous magnesium sulfate. Then, ethyl acetate was distilled off, andthe resulting oily substance was purified by chromatography on silicagel (ethyl acetate: n-hexane=1:3 v/v), and the resulting oily substancewas crystallized from ethyl acetate--n-hexane to obtain the objective3-(5-allyloxy4-bromo-2-fluorophenyl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione(5.42 g).

melting point: 123.5-124° C.

Synthesis Example 20 (Synthesis of the starting material for SynthesisExample 19) ##STR123## Ethyl 3-amino-4,4,4-trifluorocrotonate (9.66 g)was dissolved in DMF (53 ml). To this solution, a suspension of sodiummethoxide (3.11 g) in DMF was added dropwise, and the mixture wasstirred at 5° C. for 30 minutes. Then, a DMF solution of ethylN-(5-allyloxy-4-bromo-2-fluorophenyl)carbamate was added dropwisethereto, and the mixture was stirred at 130° C. for 5 hours. After thereaction, DMF was distilled off under reduced pressure, and the residuewas acidified by adding diluted hydrochloric acid thereto. This wasextracted with ethyl acetate, washed with water, and then dried overanhydrous magnesium sulfate. Then, ethyl acetate was distilled off toobtain an oily substance (18.98 g) containing the objective3-(5-allyloxy-4-bromo-2-fluorophenyl)-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione.Without being purified, this was used for the reaction of SynthesisExample 19. Synthesis Example 21 (Synthesis of the starting material forSynthesis Example 20) ##STR124## Ethyl chloroformate (5.97 g) was addeddropwise to a solution of 5-allyloxy4-bromo-2-fluoroaniline (12.3 g) andpyridine (7.90 g) in methylene chloride (100 ml) at 0° C., and themixture was stirred at 10° C. for 3 hours. After the reaction, this wasextracted with methylene chloride, then washed with diluted hydrochloricacid and an aqueous sodium hydrogencarbonate solution, and dried overanhydrous magnesium sulfate. Then, methylene chloride was distilled offto obtain to the objective ethylN-(5-allyloxy-4-bromo-2-fluorophenyl)carbamate (15.67 g).

melting point: 66-68° C.

Synthesis Example 22 (Synthesis of the starting material for SynthesisExample 2 1) ##STR125## 5-Amino-2-bromo-4-fluorophenol (30.9 g), allylbromide (21.8 g) and potassium carbonate (22.77 g) were suspended inacetonitrile (300 ml), and the mixture was stirred at room temperaturefor 12 hours. After the reaction, the precipitates were filtered, thesolvent was distilled off, and this was extracted with ethyl acetate.After washing with water, it was dried over anhydrous magnesium sulfate.Then, ethyl acetate was distilled off and the resulting oily substancewas purified by chromatography on silica gel (ethyl acetate:n-hexane=1:3) to obtain the objective 5-allyloxy-4-bromo-2-fluoroaniline(12.14 g). BIOLOGICAL TEST EXAMPLES Test Example 1 (Test ofpre-emergence soil-treatment)

Preparations of active compounds

carrier (acetone): 5 parts by weight

emulsifier (benzyloxy polyglycol ether): 1 part by weight

A preparation of active compound is obtained as an emulsion by mixingone part by weight of an active compound, the above-stated amount ofcarrier and the above-stated amount of emulsifier. A prescribed amountof this preparation is diluted with water to prepare a testing solution.

Testing procedure

In the greenhouse, seeds of Echinochloa crus-galli Beauv., Setariaviridis Beauv., Amaranthus lividus and Persicaria lapathifolia weresowed each in the surface layer of plowed land soil filled in a 120 cm²pot with soil-covering, and each a prescribed amount of the testingsolution prepared by the above method was uniformly spread on thesurface layer of soil in the testing pot. The herbicidal effect wasexamined on the day after 4 weeks from the spreading.

In this test, for example, the above compounds Nos. 3, 4, 5, 6, 7, 8,12, 17, 18, 26, 30, 31, 52, 53, 54, 59, 60, 61, 62, 64, 65 and 66 of theinvention exhibited 95% or more of the herbicidal rate againstEchinochloa crus-galli Beauv., Setaria viridis Beauv., Amaranthuslividus and Persicaria lapathifolia by the dose of 0.5 kg/ha.

Test Example 2 (Test offoliage-treatment)

In the greenhouse, seeds of Echinochloa crus-galli Beauv., Setariaviridis Beauv., Amaranthus lividus and Persicaria lapathifolia weresowed each in a 120 cm² pot filled with plowed land soil and coveredwith soil. After 10 days from the sowing and soil-covering (when theweeds were in 2-leaf stage on average), each a prescribed amount of thetesting solution prepared similarly to those in the above Test Example 1was uniformly spread on the foliage part of tested plant in the testingpot. After 3 weeks from the spreading, the herbicidal effect wasexamined.

In this test, for example, the above compounds Nos. 3, 4, 7, 8, 12, 17,26, 30, 31, 52, 53, 54, 59, 60, 61, 62, 64, 65 and 66 of the inventionexhibited 95% or more of the herbicidal rate against Echinochloacrus-galli, Setaria viridis, Amaranthus lividus and Persicarialapathifolia by the dose of 0.5 kg/ha.

We claim:
 1. Phenylacetylene derivatives of formula: ##STR126## whereinX represents hydrogen, halogen, C₁₋₆ alkyl, or C₁₋₆ haloalkyl,Yrepresents hydrogen, hydroxy, halogen, cyano, nitro, C₁₋₆ alkyl, C₁₋₆haloalkyl, C₁₋₆ alkoxy, C₃₋₈ cycloalkoxy, C₁₋₆ haloalkoxy, C₁₋₃alkoxy-C₁₋₃ alkoxy, C₁₋₆ -alkylthio, C₃₋₈ cycloalkylthio, C₁₋₆haloalkylthio, C₁₋₆ alkylsulfinyl, C₁₋₆ alkylsulfonyl, C₃₋₈cycloalkylsulfonyl C₁₋₆ haloalkylsufonyl, C₁₋₆ alkylsulfonyloxy, C₃₋₆alkenyloxy, C₃₋₆ alkyloxy, a group SO₂ NR^(a) R^(b), a group COOR^(c), agroup CONR^(d) R^(c), optionally substituted amino, a group A¹-(CH₂)n-CHR^(f) --COOR^(g), C₁₋₃ alkoxycarbonyl-C₁₋₃ alkyl or C₁₋₃alkoxycarbonyl-C₁₋₃ haloalkyl, or Y may form a 5- or 6-membered ringtogether with Z which is vicinal to the carbon atom of Y, R^(a) andR^(b) each represent independently hydrogen or C₁₋₆ alkyl or R^(a) andR^(b) may form together with the N atom to which they are bonded a 5- or6-membered heterocyclic group, R^(c) represents hydrogen, an alkalimetal, an alkaline earth metal, C₁₋₆ alkyl or C₁₋₄ alkoxy-carbonyl-C₁₋₄alkyl, R^(d) represents hydrogen or C₁₋₆ alkyl, R^(e) representshydrogen or C₁₋₆ alkyl, R^(f) represents hydrogen, halogen or C₁₋₆alkyl, R^(g) represents hydrogen, an alkali metal, an alkaline earthmetal or C₁₋₆ alkyl, A¹ represents oxygen or sulfur, n is 0 or 1, Zrepresents hydrogen or halogen, m is 1 or 2, R represents hydrogen,halogen, C₁₋₆ alkyl, hydroxy-C₁₋₆ alkyl, tri(C₁₋₆ alkyl)silyl, a groupCOOR^(c) or a group CONR^(d) R^(c), Q represents a heterocycle selectedfrom the group consisting of ##STR127## R² represents hydrogen or C₁₋₆haloalkyl, R³ represents hydrogen, cyano, halogen or C₁₋₆ allyl, R⁴represents hydrogen, amino or C₁₋₆ alkyl, R⁵ represents hydrogen, C₁₋₆alkyl, C₁₋₆ haloalkyl, C₃₋₈ cycloalkyl or C₃₋₈ alkynyl.
 2. Thephenylacetylene derivative of formula (I) ##STR128## wherein Xrepresents hydrogen, fluorine, chlorine, methyl or trifluoromethyl,Yrepresents hydrogen, hydroxy, fluorine, chlorine, cyano, nitro, methyl,ethyl, propyl, trifluoromethyl, chlorodifluoromethyl, C₁₋₃ alkoxy, C₃₋₆cycloalkoxy, C₁₋₃ haloalkoxy, C₁₋₃ alkoxy-C₁₋₃ alkoxy, C₁₋₃ alkylthio,C₃₋₆ cycloalkylthio, C₁₋₃ haloalkylthio, C₁₋₃ alkyl-sulfinyl, C₁₋₃alkyl-sulfonyl, C₃₋₆ cycloalkylsulfonyl, C₁₋₃ haloalkylsulfonyl, C₁₋₃alkyl-sulfonyl-oxy, C₃₋₄ alkenyloxy, C₃₋₄ alkynyloxy, aminosulfonyl,methyl-aminosulfonyl ethylamino-sulfonyl, diethylaminosulfonyl,1-pyrroli-dinyl-sulfonyl, a group COOR^(c), aminocarbonyl, amino,acetylamino, trifluoromethylsulfonylamino, methylsulfonylamino,ethylsulfonylamino, bis(methylsulfonyl)amino, bis(ethylsulfonyl)amino,(C₁₋₄ alkylcarbonyl)(C₁₋₄ alkyl-sufonyl)amino, C₁₋₃ alkoxycarbonyl-C₁₋₃alkylthio, C₁₋₃ alkoxy-carbonyl-C₁₋₃ haloalkyl-thio, C₁₋₃alkoxycarbonyl-C₁₋₃ alkoxy, C₁₋₃ alkoxy-carbonyl-C₁₋₃ haloalkoxy, C₁₋₃alkoxycarbonyl-C₁₋₃ -C₁₋₃ alkyl or C ₁₋₃ alkoxycarbonyl-C₁₋₃ haloalkyl,R^(c) represents hydrogen, methyl, ethyl, propyl, methoxycarbonylmethyl,ethoxycarbonylmethyl, 1-(methoxycarbonyl)ethyl or1-(ethoxy-carbonyl)ethyl, Z represents hydrogen, fluorine or chlorine,or Y may form a group --OCR^(h) R^(i) --CH₂ -- or a group --OCR^(h)═CH-- together with Z which is vicinal to the carbon atom of Y, R^(h)represents hydrogen, C₁₋₃ alkyl, hydroxy-C₁₋₃ alkyl, C₁₋₃ alkoxy-C₁₋₃alkyl, carboxy or C₁₋₃ alkoxycarbonyl, R^(i) represents hydrogen or C₁₋₃alkyl, m is 1 or 2, R represents hydrogen, fluorine, methylhydroxymethyl, trimethylsilyl, methoxycarbonyl, ethoxycarbonyl oraminocarbonyl, Q represents a heterocycle selected from the groupconsisting of ##STR129## R² represents hydrogen, trifluoromethyl,difluoromethyl, chlorodifluoromethyl, 2,2,2-trifluoroethyl,3-fluoro-propyl, 3,3,3-trifluoropropyl, 2,2,3,3-tetrafluoropropyl or1,1,2,3,3,3-hexafluoropropyl R³ represents hydrogen, cyano, fluorine,chlorine, methyl or ethyl, R⁴ represents hydrogen, amino, methyl orethyl, R⁵ represents hydrogen, methyl, ethyl, isopropyl, tert-butyl,1-ethyl-1-methylpropyl, 1,1-dimethylpropyl, chloromethyl,difluoromethyl, dichlorofluoromethyl, trifluoromethyl, 3-fluoropropyl,1,1-dimethyl-2-chloroethyl, 1,1-dimethyl-2-fluoroethyl, cyclopropyl or1,1-dimethylpropargyl.
 3. The phenylacetylene derivatives according toclaim 1, whereinX represents hydrogen or fluorine, Y representshydrogen, hydroxy, fluorine, chlorine, cyano, nitro, methyl,trifluoromethyl, methoxy, ethoxy, isopropoxy, cyclopropoxy,cyclopentyloxy, cyclohexyloxy, difluoromethoxy, chlorodifluoromethoxy,trifluoromethoxy, methoxymethoxy, methylthio, ethylthio, isopropylthio,propylthio, cyclopropylthio, cyclopentylthio, difluoromethylthio,chlorodifluoromethylthio, trifluoromethylthio, methylsulfinyl,methylsulfinyl, isopropylsulfonyl, cyclopropylsulfonyl,cyclopentylsulfonyl, difluoromethylsulfonyl,chlorodifluoromethylsulfonyl, trifluoromethylsulfonyl,methylsulfonyloxy, allyloxy, 2-methylallyloxy, propargyloxy,aminosulfonyl, methylaminosulfonyl, ethylaminosulfonyl, a groupCOOR^(c), aminocarbonyl, amino, methylsulfonylamino, ethylsulfonylamino,bis(methylsulfonyl)amino, bis(ethylsulfonyl)amino,(acetyl)(ethylsulfonyl)amino, (tert-butyl-carbonyl)(methylsulfonyl)amino, (tert-butylcarbonyl)(ethylsulfonyl)amino,1-(methoxycarbonyl)ethylthio, ethoxycarbonylmethylthio,methoxycarbonylmethylthio, 1-(ethoxycarbonyl)ethoxy,1-(methoxycarbonyl)ethoxy, ethoxycarbonylmethoxy,methoxycarbonylmethoxy, 2-(ethoxycarbonyl)-2-chloro-ethoxyethoxycarbonylmethyl or 2-(ethoxycarbonyl)-2-chloroethyl, R^(c)represents hydrogen, methyl ethyl propyl, isopropyl,methoxycarbonylmethyl, ethoxycarbonylmethyl, 1-(methoxycarbonyl)ethyl or1-(ethoxy carbonyl)ethyl, A¹ represents oxygen or sulfur, n is 0 or 1, Zrepresents hydrogen, fluorine or chlorine, m is 1, R representshydrogen, hydroxymethyl, fluorine, trimethylsilyl, methoxycarbonyl orethoxycarbonyl, Q represents a heterocycle selected from the groupconsisting of ##STR130## R² represents hydrogen trifluoromethyl,difluoromethyl, chlorodifluoromethyl or 3-fluoropropyl, R³ representshydrogen, cyano, fluorine, chlorine or methyl, R⁴ represents hydrogen,amino or methyl, R⁵ represents hydrogen, methyl, ethyl, isopropyl,tert-butyl, chloromethyl difluoromethyl, trifluoromethyl, 3-fluoropropylor cyclopropyl.
 4. A herbicidal composition comprising a herbicidallyeffective amount of a compound according to claim 1 and a diluent.
 5. Amethod of combatting unwanted vegetation which comprises administeringto such vegetation or to a locus from which it is desired to excludesuch vegetation a herbicidally effective amount of a compound accordingto claim 1.